CN110391428B - 自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料及其制备方法和应用 - Google Patents
自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料及其制备方法和应用 Download PDFInfo
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- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 claims description 5
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Abstract
本发明公开一种自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料及其制备方法和应用,属于燃料电池技术领域,针对目前的过渡金属化合物作为HER催化剂时高的催化活性和良好稳定性不能兼具,以及制备方法复杂等问题,本发明以在碳布上自组装生成的自支撑(NH4)4[NiH6Mo6O24]·5H2O多酸盐为前驱物,在氩氢气体(Ar/H2=5/5)的气氛下通过两步程序升温热处理制得。该复合材料作为燃料电池的阳极材料催化剂具有优异的析氢反应催化活性,在达到150mAcm‑2的电流密度下仅需要148mV过电势,优于Mo/Ni3Mo3N(204mV)和Mo/Mo2N(295mV),比商用Pt/C墨汁(4mg/ml)低37mV。本发明为进一步提高燃料电池的综合性能,尤其是阳极析氢反应性能提供了新的方法和思路。
Description
技术领域
本发明涉及自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料的制备及其作为燃料电池阳极反应催化剂的应用。
背景技术
由于能源危机和环境污染问题的日益严峻,人们对新能源的关注越来越多。氢能作为一个无污染且具有高能量密度的特点,在众多新能源中脱颖而出。如果实现氢能的大规模应用,将会使人类社会进入一个可持续发展的绿色时代,然而要实现氢能的大规模应用必将减少制氢成本。在众多产氢方法中电解水产氢被认为是未来最经济有效的方法。贵金属基催化剂目前仍然是析氢反应(HER)的最有效催化剂,但由于其昂贵的价格和地球中的有限含量限制了贵金属基催化剂的大规模商业化使用。另一方面,析氢反应虽然是只有两个电子转移的简单反应,但多种元素参与反应产生较大能垒,导致析氢反应动力学缓慢。因此如何降低催化反应的过电位,降低工作电压减少能耗增加反应动力学成为另一研究热点。目前研究人员在利用非贵金属替代贵金属催化剂和提高催化性能方面已经做了大量研究,取得很大进展,许多合金和过渡金属化合物作为HER催化剂都表现出良好的性能。但也有一些未能完全解决的问题,如制作工艺繁琐,高的催化活性和良好稳定性不能兼具等。多金属氧酸盐(POMs)是非常有吸引力的电催化化合物由于它们适当且可调的氧化还原属性和具有多个特征氧化态和快速逐步电子转移。因此近些年来在多金属氧酸盐和修饰的多金属氧酸盐作为电催化的研究也取得很大进步。
发明内容
本发明的目的是提供一种自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料的制备方法及其作为燃料电池阳极反应催化剂的应用。该发明通过以多金属氧酸盐为前驱体通过过溶液饱和溶液析出和两步氢还原和原位氮化热处理的方法制备了自支撑纳米多孔Mo/Mo2N@Ni3Mo3N 复合材料。该复合材料简单的制作方法提供一个新的一体化电极合成思路,其中Mo/Mo2N@Ni3Mo3N为具有双模式孔的垂直于碳布生长的片状结构,其片的大小约为 10~30μm,厚度约1~3μm,其中垂直生长的结构有利于暴露出更多的电化学活性位,独特的双模式孔结构特性使其具有较快的电极表面电化学反应速度和电极内部的氢原子扩散速度,复合材料中Mo2N和Ni3Mo3N的协同作用,大大提高了其析氢反应电化学活性和电化学稳定性。
本发明涉及一种自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料的制备方法及其作为燃料电池阳极反应催化剂的应用。
具体内容如下:
一种自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料的制备方法,包括以下步骤:
a、2.45~2.55g四水合七钼酸铵((NH4)6Mo7O24·4H2O)溶于40mL去离子水中,在350℃的加热板上加热至沸腾,然后将10mL含有0.45~0.46g六水合硫酸镍(Ⅱ)(NiSO4·6H2O)的溶液加入到上述沸腾溶液中,继续加热至溶液剩余8~12mL,获得过饱和 (NH4)4[NiH6Mo6O24]·5H2O多酸盐溶液,析出的晶体形貌为片状,大小约10~30μm,厚度约 1~3μm;
b、预先处理碳布改善其亲水性,将碳布放在浓硝酸中90~120℃回流2~2.5h;将a述剩余溶液趁热过滤并倒入含有1.0cm×0.5cm尺寸大小的碳布的烧杯中,室温下自然冷却并继续使多酸盐生长2.5~3.5h后取出碳布,在60℃干燥,获得自支撑(NH4)4[NiH6Mo6O24]·5H2O 多酸盐;
c、将干燥好的自支撑(NH4)4[NiH6Mo6O24]·5H2O多酸盐在氩氢混合气体(Ar/H2=95/5)气氛下用退火炉经过两步升温还原处理:
首先在450~550℃下保温2.5~3.5h,然后在800~850℃下保温2.5~3.5h,升温速率3~8℃ /min,热处理结束后随炉冷却至室温,自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料制备完成。
根据上述制备方法得到的自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料,其作为电极材料进行电化学测试,包括以下步骤:
a、将步骤1中所制备的自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料直接作为工作电极,碳棒作为对电极,饱和甘汞电极(Hg/Hg2Cl2,SCE)作为参比电极,1mol/L的KOH溶液作为电解液,组成标准的三电极系统进行电化学测试;
b、用所述所制备的自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料作为工作电极进行析氢电化学性能(HER)测试时,极化曲线(LSV)扫描速率在1mV/s,电化学阻抗(EIS)在过电势0.1V频率范围100kHz到10mHz;
d、用所述自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料作为工作电极进行电化学性能测试时,在进行双电层电容测试时所选用10,20,30,40和50mV/s;
e、所述电极材料所制备的自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料作为工作电极,稳定性测试进行40h的电压-时间曲线的测试;
以上测试结果证明所述电极材料所制备的自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料作为燃料电池阳极反应催化剂具有优异的析氢反应催化性能和良好的稳定性。
本发明的技术效果是:
本发明制得的自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料具有独特的双模式孔结构、高的导电性、快的电子和离子传输速度,快的电极表面电化学反应速度和电极内部的氢原子扩散速度,以及Mo2N和Ni3Mo3N之间的协同作用显著提高了其析氢反应电化学性能和稳定性。
附图说明
图1、不同材料的析氢反应电化学性能极化曲线。
图2、自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料合成步骤示意图。
图3a和图3b、前驱体自组装(NH4)4[NiH6Mo6O24]·5H2O多酸盐的SEM图片;
图3c、自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料的SEM图片;
图3d、Mo/Ni3Mo3N的SEM图片;
图3e、Mo/Mo2N的SEM图片。
图4a、前驱体自组装(NH4)4[NiH6Mo6O24]·5H2O多酸盐的XRD图谱;
图4b、自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料的XRD图谱;
图4c、Mo/Ni3Mo3N的XRD图谱;
图4d、Mo/Mo2N的XRD图谱。
图5、自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料的TEM图片。
图6、自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料的HR-TEM图片。
图7、不同材料的Tafel斜率。
图8a、拟和EIS图谱的等效电路;
图8b、不同材料的EIS电化学阻抗图谱;
图8c、不同材料的溶液电阻(RS)和电荷转移电阻(RCT)值。
图9a、自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料的双电层区域的循环伏安曲线;
图9b、Mo/Ni3Mo3N的双电层区域的循环伏安曲线;
图9c、Mo/Mo2N的双电层区域的循环伏安曲线;
图9d、根据循环伏安曲线计算的各材料的双电层电容(Cdl)。
图10、自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料的不同电流密度下电压-时间测试。
图11a、自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料电压-时间40h测试前后极化曲线;
图11b、电压-时间40h测试后SEM图片。
图12、自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料电压-时间40h测试前后XRD图谱。
具体实施方式
实施例1
本实施例中的制备过程和步骤如下:
a、2.50g四水合七钼酸铵((NH4)6Mo7O24·4H2O)溶于40mL去离子水中在350℃加热至沸腾,然后将10mL含有0.457g六水合硫酸镍(Ⅱ)(NiSO4·6H2O)的溶液加入到上述沸腾溶液中,继续加热至溶液剩余10mL,获得过饱和(NH4)4[NiH6Mo6O24]·5H2O多酸盐溶液,析出的晶体形貌为片状,大小约20μm,厚度约2μm;
b、预先处理碳布改善其亲水性,将上述剩余溶液趁热过滤并倒入含有1.0cm×0.5cm尺寸大小的碳布的烧杯中,室温下自然冷却并继续使多酸盐生长三小时后取出碳布,在60℃干燥,自支撑(NH4)4[NiH6Mo6O24]·5H2O多酸盐获得;
c、将干燥好的自支撑(NH4)4[NiH6Mo6O24]·5H2O多酸盐在氩氢混合气体(Ar/H2=95/5)气氛下用退火炉经过两步升温还原处理:
首先在500℃下保温3h,然后在800℃下保温3h,升温速率5℃/min,热处理结束后随炉冷却至室温,自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料制备完成。
材料的形貌和结构表征
通过扫描电镜(SEM)表征,前驱体自支撑(NH4)4[NiH6Mo6O24]·5H2O多酸盐,自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料,Mo/Mo2N,Mo/Ni3Mo3N的SEM图片分别见图3a-图3e。如图3a和图3b所示,自组装(NH4)4[NiH6Mo6O24]·5H2O多酸盐表现为片状结构垂直生长在碳布上。图3c的自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料表现出双模式孔的片状结构,图3d的Mo/Mo2N表现为颗粒堆积形成的单孔结构,图3e的Mo/Ni3Mo3N表现为片状的单模式孔结构。
图4a-图4d为前驱体自支撑(NH4)4[NiH6Mo6O24]·5H2O多酸盐,自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料,Mo/Mo2N,Mo/Ni3Mo3N的XRD图谱,从XRD图谱中都能证明各种成分的存在。从图5的自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料的TEM图片中也可以证明有小孔的存在。图6的自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料的 HR-TEM图片分别展示了Mo晶格间距0.222nm,对应Mo(110)晶面,Mo2N晶格间距0.208nm,对应Mo(200)晶面,Ni3Mo3N晶格间距0.221nm,对应Mo(221)晶面。
实施例2
将实施例1所制备的自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料直接作为工作电极,碳棒作为对电极,饱和甘汞电极(Hg/Hg2Cl2,SCE)作为参比电极,1mol/L的KOH溶液作为电解液,组成标准的三电极系统进行电化学测试;
用实施例1所制备的自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料作为工作电极进行析氢电化学性能(HER)测试时,极化曲线(LSV)扫描速率在1mV/s,电化学阻抗(EIS)在过电势0.1V频率范围100kHz到10mHz;
用实施例1所制备的自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料作为工作电极进行电化学性能测试时,在进行双电层电容测试时所选用10,20,30,40和50mV/s;
用实施例1所制备的自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料作为工作电极,稳定性测试进行40h的电压-时间曲线的测试;
材料的电化学性能表征结果
通过图1的不同材料的极化曲线测试,在自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料的起始电位约为20mV,高于Pt/C 0mV,但低于Mo/Ni3Mo3N的36mV和Mo/Mo2N的91mV。在达到电流密度150mA cm-2下,自支撑纳米多孔Mo/Mo2N@Ni3Mo3N所需要过电势148mV,低于Mo/Ni3Mo3N的204mV和Mo/Mo2N的295mV,并且低于Pt/C的185mV。图7分别表示不同材料的Tafel斜率,自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料(61mV dec-1)有着和 Pt/C(64mV dec-1)相近的Tafel斜率,远小于Mo/Ni3Mo3N(112mV dec-1)和Mo/Mo2N(122mV dec-1),表明自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料拥有较好的析氢反应动力学。如图 8a-图8c所示,表现了不同材料的EIS电化学阻抗图谱,从图中可以看出虽然三种材料具有相似的溶液电阻(自支撑纳米多孔Mo/Mo2N@Ni3Mo3N 2.5Ω,Mo/Ni3Mo3N 2.4Ω,Mo/Mo2N 3.0 Ω),但自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料电荷转移电阻(3.6Ω),小于 Mo/Ni3Mo3N(8.0Ω),并且远小于Mo/Mo2N(36.5Ω),表明自支撑纳米多孔Mo/Mo2N@Ni3Mo3N 拥有良好的电子转移性能。图9a-图9d表明不同材料的双电层区域的循环伏安曲线和双电层电容(Cdl),其中自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料拥有最高的Cdl值(104mF cm-2),相比于Mo/Ni3Mo3N(63mF cm-2)和Mo/Mo2N(20mF cm-2),表明自支撑纳米多孔 Mo/Mo2N@Ni3Mo3N复合材料拥有更高的电化学活性面积。图10为自支撑纳米多孔 Mo/Mo2N@Ni3Mo3N复合材料分别在10,50,100and 150mAcm-2的电流密度下电压-时间连续稳定性测试。图11a为自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料电压-时间40h测试前后极化曲线,由极化曲线表明经过40h电压-时间测试前后,复合材料的催化活性几乎没有任何衰减,表明良好的电催化稳定性。图12为自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料电压-时间40h测试前后XRD图谱,由图谱表明测试前后自支撑纳米多孔Mo/Mo2N@Ni3Mo3N 复合材料的化学组成未发生变化,插图的SEM图片表明测试后的复合材料中的小孔仍然存在,表明复合材料的良好结构稳定性。该复合材料可作为燃料电池的阳极反应催化剂,在未来燃料电池领域具有很好的应用前景。本发明涉及的制备方法还可以拓展到其他金属基体系,为进一步提高析氢反应性能提供了新的方法和思路。
Claims (4)
1.一种自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料,其特征在于,Mo/Mo2N@Ni3Mo3N为具有双模式孔的垂直于碳布生长的片状结构,其片的大小为10~30μm,厚度1~3μm,其制备方法如下:
a、2.45~2.55g四水合七钼酸铵溶于40 mL去离子水中,在350 ℃的加热板上加热至沸腾, 然后将10mL含有0.45~0.46g 六水合硫酸镍(Ⅱ)的水溶液加入到上述沸腾溶液中,继续加热至溶液剩余8~12 mL,获得过饱和 (NH4)4[NiH6Mo6O24]∙5H2O多酸盐溶液;
b、预先处理碳布改善其亲水性,将碳布放在浓硝酸中90~120℃回流2~2.5h;将a述剩余溶液趁热过滤并倒入含有1.0 cm×0.5 cm 尺寸大小的碳布的烧杯中,室温下自然冷却并继续使多酸盐生长2.5~3.5h后取出碳布,在60℃干燥,获得自支撑(NH4)4[NiH6Mo6O24]∙5H2O多酸盐;
c、将干燥好的自支撑(NH4)4[NiH6Mo6O24]∙5H2O多酸盐在氩氢混合气体Ar/H2体积比=95/5气氛下用退火炉经过两步升温还原处理:
首先在450~550℃下保温2.5~3.5h,然后在800~850℃下保温2.5~3.5h,两步升温过程中的升温速率3~8℃/min,热处理结束后随炉冷却至室温,自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料制备完成。
2.如权利要求1所述的自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料的制备方法,其特征在于,该方法包括以下步骤:
a、2.45~2.55g四水合七钼酸铵溶于40 mL去离子水中,在350 ℃的加热板上加热至沸腾, 然后将10mL含有0.45~0.46g 六水合硫酸镍(Ⅱ)的水溶液加入到上述沸腾溶液中,继续加热至溶液剩余8~12 mL,获得过饱和 (NH4)4[NiH6Mo6O24]∙5H2O多酸盐溶液;
b、预先处理碳布改善其亲水性,将碳布放在浓硝酸中90~120℃回流2~2.5h;将a述剩余溶液趁热过滤并倒入含有1.0 cm×0.5 cm 尺寸大小的碳布的烧杯中,室温下自然冷却并继续使多酸盐生长2.5~3.5h后取出碳布,在60℃干燥,获得自支撑(NH4)4[NiH6Mo6O24]∙5H2O多酸盐;
c、将干燥好的自支撑(NH4)4[NiH6Mo6O24]∙5H2O多酸盐在氩氢混合气体Ar/H2体积比=95/5气氛下用退火炉经过两步升温还原处理:
首先在450~550℃下保温2.5~3.5h,然后在800~850℃下保温2.5~3.5h,两步升温过程中的升温速率3~8℃/min,热处理结束后随炉冷却至室温,自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料制备完成。
3.根据权利要求2所述的自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料的制备方法,其特征在于,步骤a中四水合七钼酸铵为2.50g,六水合硫酸镍(Ⅱ)为0.457 g。
4.根据权利要求2所述的自支撑纳米多孔Mo/Mo2N@Ni3Mo3N复合材料的制备方法,其特征在于,
步骤c中首先在500℃下保温3h,然后在800℃下保温3h,两步升温过程中的升温速率5℃/min。
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