CN108097269B - 一种超薄多孔Ce-Ni-O-S纳米片及其制备方法和应用 - Google Patents
一种超薄多孔Ce-Ni-O-S纳米片及其制备方法和应用 Download PDFInfo
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- 229910000667 (NH4)2Ce(NO3)6 Inorganic materials 0.000 claims description 7
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Abstract
本发明公开一种超薄多孔Ce‑Ni‑O‑S纳米片及其制备方法和应用,属于纳米领域。本发明的超薄多孔Ce‑Ni‑O‑S纳米片主要元素是Ce、Ni、O和S,为不规则的超薄片状结构,具有多孔结构,且具有较多位错,台阶缺陷位点,Ce、Ni、O和S均匀分布在六边形片上,具有优异的OER性能,优于目前市售的IrO2。本发明采用“一锅煮”方法,利用程序控温模式得到超薄多孔Ce‑Ni‑O‑S纳米片,工艺简单,反应温度低,时间短,适合于批量生产,对于可再生能源技术发展具有重要的指导意义。
Description
技术领域
本发明涉及一种超薄多孔Ce-Ni-O-S纳米片及其制备方法和应用,属于纳米领域。
背景技术
随着全球经济的发展,每个人都更加依赖能源。至今为止,我们需求的大部分能源还是来自传统的化石燃料(煤、石油和天热气等),而这些能源是不可持续的,只有有限的储备。严峻的能源危机和由化石能源消费产生的环境污染,日益危及人类社会可持续发展,研发高效低成本绿色储能技术和新能源迫在眉睫。
燃料电池兼具高能效、无噪声、无污染、可连续稳定工作等特点,被认为是21世纪最有发展前景的新能源技术。将普通H2-O2燃料电池和水电解池按一定的方式组合得以循环进行,即构成可再生H2-O2燃料电池。在水电解池中,将H2O送入电解装置,输入电能,H2O分解生成H2和O2,涉及阳极析氧反应(Oxygen Evolution Reaction, OER),将电能以化学能的方式储存起来。在阳极上发生OER时所需的理论电压为1.23 V。然而在商业化水分解的体系中,水的全分解需要电压1.8-2.0 V,才能驱动水分解产生清洁能源。因此采用高效催化水分解的催化剂能够大大降低水分解的过电势。尽管IrO2和RuO2也是目前催化OER性质最好的电催化剂,然而缺点在于IrO2和RuO2价格昂贵,进一步限制了催化剂的商业化应用。
文献研究表明,OER因较强O=O键,需要多步电子传递及转移,导致动力学缓慢,催化剂的过电位过高。因此在设计燃料电池的过程中,降低OER的过电位成为商业化应用的关键。当今纳米技术的发展给新型可再生型H2-O2燃料电池电催化剂的设计带来新契机。在过去的几年里,科学家们也一直致力于开发具有高性能、高选择性、高稳定性及低成本的纳米催化剂。同时值得注意的是,引入一种或者多种金属在结构缺陷处的诱导选择性生长,进一步促进了多组分金属纳米晶表界面几何结构和电子结构的调控,为优化催化反应提供了较大空间。例如Strickler课题组可控合成的核壳Au@金属氧化物纳米晶(Au@MxOy,M = Ni,Co,Fe和CoFe),以OER为探针反应,电化学测试表明,Au@CoFeOx因Au和金属氧化物之间的耦合效应,提高了催化剂的催化活性和稳定性。
因此,研发高效的多元纳米晶催化剂是目前的研究热点;在可再生能源技术的发展过程中,寻求高效廉价、特殊结构的合金纳米晶,特别是可用于OER的电催化剂具有重要意义和巨大挑战。
发明内容
发明目的:本发明目的之一在于针对现有技术的不足,提供一种应用于燃料电池析氧反应中的新型、高效、廉价的OER催化剂Ce-Ni-O-S纳米片。
为了实现这一目的,本发明公开了一种超薄多孔Ce-Ni-O-S纳米片,所述Ce-Ni-O-S纳米片主要元素是Ce、Ni、O和S,为不规则的超薄片状结构,具有多孔结构,且具有较多位错,台阶缺陷位点,Ce、Ni、O和S均匀分布在六边形片上。
进一步地,本发明还公开了这种Ce-Ni-O-S纳米片的制备方法。
具体的技术方案如下:
一种Ce-Ni-O-S纳米片的制备方法:将(NH4)2Ce(NO3)6,Ni(NO3)2 . 6H2O,CS(NH2)2加入到十二胺(DDA)、十八碳烯(ODE)及油酸(OA)溶液中,逐步升温至280℃,并保温反应得到含有Ce-Ni-O-S纳米片的产物,经分散沉降、离心分离得到Ce-Ni-O-S纳米片。
优选地,每份Ce-Ni-O-S纳米片的各组分的添加比例为:(NH4)2Ce(NO3)6 0.1 mmol,Ni(NO3)2 . 6H2O 0.5 mmol,CS(NH2)2 3 mmol,DDA 5 mL,ODE 5 mL,OA 3 mL。
优选地,升温过程直接升温至280℃或者按照3~10℃ min-1的升温速率逐步升温。
进一步地,升温过程按照4~8℃ min-1的升温速率逐步升温。
进一步地,直接升温至280℃,并维持此温度反应得到含有Ce-Ni-O-S纳米片的产物。
优选地,反应后含有Ce-Ni-O-S纳米片的产物用体积比1:1的无水乙醇和正庚烷混合分散沉降。其中采用无水乙醇和正庚烷分散沉降、离心分离的操作可以重复3-4次。
优选地,保温反应时间为30 min。当温度达到我们所期待的温度后,保持温度恒定并反应30 min。譬如,当温度达到280℃后,反应30 min。
同时本发明还公开了这一超薄多孔Ce-Ni-O-S纳米片作为燃料电池催化剂的应用。特别是这一Ce-Ni-O-S纳米片作为燃料电池的析氧反应催化剂的应用。
本发明所制得的超薄多孔Ce-Ni-O-S纳米片采用X射线能谱仪(EDS)和mapping来表征其组份和结构;用透射电子显微镜(TEM)、高分辨透视电子显微镜(HRTEM)、扫描透视电子显微镜(STEM)分析其尺寸、形貌和微结构等。
有益效果:(1)本发明所制得的Ce-Ni-O-S纳米片具有优异的OER性能,能够高效催化燃料电池中的OER。经检测其性能优于目前市售的IrO2,对于可再生能源技术发展具有重要的指导意义。
(2)本发明中所涉及的Ce-Ni-O-S纳米片通过固液相化学反应制备,在常压和较低的温度下可控地合成了Ce-Ni-O-S纳米片,同时由于采用“一锅煮”的方式,利用程序控温模式得到具有独特超薄多孔Ce-Ni-O-S纳米片,工艺简单,反应温度低,时间短,适合于批量生产。
附图说明
图1为本发明制备的超薄多孔Ce-Ni-O-S纳米片的EDS图。
图2为本发明制备的超薄多孔Ce-Ni-O-S纳米片的TEM图。
图3 为本发明制备的超薄多孔Ce-Ni-O-S纳米片的HRTEM图。
图4 为本发明制备的超薄多孔Ce-Ni-O-S纳米片的STEM图。
图5 为本发明制备的超薄多孔Ce-Ni-O-S纳米片的mapping图。
图6为本发明制备的超薄多孔Ce-Ni-O-S纳米片的OER性能测试图。
具体实施方式
下面通过附图对本发明技术方案进行详细说明,但是本发明的保护范围不局限于所述实施例。
实施例1
室温下,称量55 mg(0.1 mmol)(NH4)2Ce(NO3)6,145 mg(0.5 mmol)Ni(NO3)2 . 6H2O,228 mg(3 mmol)CS(NH2)2粉末,并将全部原料一起加入到干燥的容量为250 mL的三颈圆底烧瓶中,再用量筒分别量取5 mL DDA,5 mL ODE,3 mL OA,加入到三颈圆底烧瓶中,超声并搅拌至完全溶解,得到溶液。
将三颈圆底烧瓶转移至沙浴中,程序控温下以8℃/min的速率升温至280℃下保温30 min,至反应结束。待反应器自然冷却至室温,加入适量体积比1:1混合的正庚烷和乙醇分散,离心分离固体。将固体洗涤后得到黑色产物,在真空干燥箱里真空干燥过夜后,用于分析表征。
采用EDS,mapping,TEM和STEM测试分别对产品进行分析,结果如图1至图5所示。图1显示主要元素是Ce、Ni、O和S,图面上还有少量C、Si和Cu的峰,来自测试的铜网。图2为样品的TEM图,从图中可以看出样品为不规则的超薄片状结构,且具有多孔结构。图3为单一颗粒的HRTEM图,从图中可以看出样品为多孔结构,且具有较多位错,台阶等缺陷位点,文献研究表明,缺陷位点对提高催化活性具有重要作用。图4为样品的STEM图,从图中可以看出样品为多孔片状结构。图5为样品的mapping图,从图中可以看出Ce、Ni、O和S均匀分布在六边形片上。
因此,基于上述分析可知,我们所得到的晶体产物是Ce-Ni-O-S纳米片,为超薄介稳定态多孔结构。
实施例2
室温下,称量55 mg(0.1 mmol)(NH4)2Ce(NO3)6,145 mg(0.5 mmol)Ni(NO3)2 . 6H2O,228 mg(3 mmol)CS(NH2)2粉末,并将全部原料一起加入到干燥的容量为250 mL的三颈圆底烧瓶中,再用量筒分别量取5 mL DDA,5 mL ODE,3 mL OA,加入到三颈圆底烧瓶中,超声并搅拌至完全溶解,得到溶液。
将三颈圆底烧瓶转移至沙浴中,程序控温下以4℃/min的速率升温至280℃下保温30 min,至反应结束。待反应器自然冷却至室温,加入适量体积比1:1混合的正庚烷和乙醇分散,离心分离固体。将固体洗涤后得到黑色产物,在真空干燥箱里真空干燥过夜。
实施例3
室温下,称量55 mg(0.1 mmol)(NH4)2Ce(NO3)6,145 mg(0.5 mmol)Ni(NO3)2 . 6H2O,228 mg(3 mmol)CS(NH2)2粉末,并将全部原料一起加入到干燥的容量为250 mL的三颈圆底烧瓶中,再用量筒分别量取5 mL DDA,5 mL ODE,3 mL OA,加入到三颈圆底烧瓶中,超声并搅拌至完全溶解,得到溶液。
将三颈圆底烧瓶转移至沙浴中,直接升温至280℃下保温30 min,至反应结束。待反应器自然冷却至室温,加入适量正庚烷和乙醇分散,离心分离固体。将固体洗涤后得到黑色产物,在真空干燥箱里真空干燥过夜。
实施例4
在三电极体系中通过循环伏安法和极化曲线法,测试样品的电化学性质,具体过程如下:
电化学实验在AUTOLAB-PGSTAT302N型电化学工作站上进行,采用标准的三电极测试体系,相应的工作电极为本文所获取的样品修饰的玻碳电极,对电极为铂片,参比电极为银/氯化银(Ag/AgCl)。本文中所有的电势均相对于Ag/AgCl。电解液为0.1 M的KOH溶液。所有电化学测试均在25℃下进行。每次实验时,所有的修饰电极均在0.1 M KOH溶液中进行测试。
样品修饰电极的制备方法如下:
每次实验前,将直径为5 mm 的旋转圆盘电极依次用1.0 μm、0.3 μm和0.05 μm 的Al2O3 粉磨至镜面,然后超声清洗,最后用二次蒸馏水淋洗干净,在室温N2气氛下干燥待用。将8 mg的超薄多孔Ce-Ni-O-S纳米片分散到1 mL乙醇中,然后加入3mL水,获得2 mg mL-1的超薄多孔Ce-Ni-O-S纳米片的悬浮液。先后将25µL此悬浮液和5 µL 1%萘酚溶液,分散在旋转圆盘电极表面N2氛围中干燥,得到超薄多孔Ce-Ni-O-S纳米片修饰电极。
OER测试前,先向溶液中通入高纯O2 30 min,以除去溶液中溶解的其它气体,并在实验过程中继续通O2以保持溶液的O2氛围。LSV也是在O2氛围中进行,相应的电化学扫描速率为10 mV/s,转速设定为1600 rpm,扫描范围为0 V-1.0 V。
检测结果如图6所示。测试结果表明,超薄多孔Ce-Ni-O-S纳米片的催化活性及稳定性优于市售IrO2催化剂。
如上所述,尽管参照特定的优选实施例已经表示和表述了本发明,但其不得解释为对本发明自身的限制。在不脱离所附权利要求定义的本发明的精神和范围前提下,可对其在形式上和细节上作出各种变化。
Claims (7)
1.一种超薄多孔Ce-Ni-O-S纳米片,其特征在于,所述的Ce-Ni-O-S纳米片主要元素是Ce、Ni、O和S,为不规则的超薄片状结构,具有多孔结构,且具有较多位错,台阶缺陷位点,Ce、Ni、O和S均匀分布在六边形片上;
所述Ce-Ni-O-S纳米片的制备方法包括以下步骤:将(NH4)2Ce(NO3)6,Ni(NO3)2 . 6H2O,CS(NH2)2加入到十二胺(DDA)、十八碳烯(ODE)及油酸(OA)溶液中,逐步升温至280℃,并保温反应得到含有Ce-Ni-O-S纳米片的产物,经分散沉降、离心分离得到Ce-Ni-O-S纳米片。
2.根据权利要求1所述的Ce-Ni-O-S纳米片,其特征在于,每份Ce-Ni-O-S纳米片的各组分的添加比例为:(NH4)2Ce(NO3)6 0.1 mmol,Ni(NO3)2 . 6H2O 0.5 mmol,CS(NH2)2 3 mmol,DDA 5 mL,ODE 5 mL,OA 3 mL。
3.根据权利要求1所述的Ce-Ni-O-S纳米片,其特征在于,升温过程直接升温至280℃或者按照3~10℃ min-1的升温速率逐步升温。
4.根据权利要求1或3所述的Ce-Ni-O-S纳米片,其特征在于,升温过程按照4~8℃ min-1的升温速率逐步升温。
5.根据权利要求1所述的Ce-Ni-O-S纳米片,其特征在于,反应后含有Ce-Ni-O-S纳米片的产物用体积比1:1的无水乙醇和正庚烷混合分散沉降。
6.根据权利要求1所述的Ce-Ni-O-S纳米片,其特征在于,保温反应时间为30 min。
7.权利要求1所述的Ce-Ni-O-S纳米片作为燃料电池的析氧反应催化剂的应用。
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