CN114917928B - 一种星形的铂铁镍铜钌多元合金固溶体多功能电催化材料及其制备与应用 - Google Patents
一种星形的铂铁镍铜钌多元合金固溶体多功能电催化材料及其制备与应用 Download PDFInfo
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- 239000006104 solid solution Substances 0.000 title claims abstract description 37
- -1 platinum-iron-nickel-copper-ruthenium Chemical compound 0.000 title claims abstract description 21
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- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 claims abstract description 9
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Abstract
本发明属于电催化材料的技术领域，公开了一种星形的铂铁镍铜钌多元合金固溶体多功能电催化材料及其制备与应用。方法：1)将十六烷基氯化铵分散于油胺中，获得分散液；将乙酰丙酮铂、乙酰丙酮铁、乙酰丙酮钌、乙酰丙酮镍、乙酰丙酮铜、碳纳米管、葡萄糖以及Mo(CO)6分散于分散液中，获得混合分散液；2)将混合分散液进行加热处理，获得星形的铂铁镍铜钌多元合金固溶体多功能电催化材料。本发明的方法简单，成功制备出具有星状形貌的多元合金固溶体电催化材料；本发明的电催化材料具有优异的HER、OER和ORR电催化性能和较好的稳定性。本发明的电催化材料用于锌空电池、电解水制氢和/或氢氧燃料电池。
Description
技术领域
本发明属于电催化材料技术领域，具体涉及一种星形的铂铁镍铜钌多元合金固溶体多功能电催化材料及其制备方法与应用。
背景技术
长期使用化石燃料造成的能源危机和环境危机越来越得到重视，开发可持续的能源材料和绿色纳米技术来制造燃料电池、金属-空气电池和水分解系统成为当下的迫切需求。电化学析氢反应(HER)、析氧反应(OER)和氧还原反应(ORR)是可再生能源技术的核心，优质的催化剂可以降低电化学反应的过电位，加快反应速率，提高其催化性能。
然而，开发高效、稳定的电催化剂仍然具有挑战性。与单金属催化剂相比，双金属和三金属合金催化剂具有更强的电催化性能和可调空间，且通过合金化来定制结合能可以诱导电子的相互作用而优化活性。高熵合金(HEAs)作为催化材料在过去的几年中引起了广泛的关注，其在合成复杂的固溶体材料中形成了大量不同的多元素活性位点，为催化剂设计提供了新的、独特的概念，减少了现有的限制，改变了对构效关系的看法，且高熵合金具有超丰富的元素组合和元素配比，其催化结合能几乎能够以连续的形式进行调控，不同的元素配位环境提供了多类型催化反应的活性位点，更具备开发多功能型催化剂的潜力。
目前，Pt贵金属仍是ORR和HER最有效的电催化剂，而IrO2和RuO2对OER具有较高活性。然而，这些铂类金属稀缺性、高成本和耐受性差的特点，阻碍了其可持续发展应用。因此，可以引入地球储量丰富、廉价的过渡金属元素，如镍、铁和铜等，与Pt族贵金属组成高熵合金，不仅可以调节合金固溶体催化剂的形貌、电子结构，提高其催化活性及稳定性，同时降低催化剂成本。然而，大多数高熵合金催化剂都是在块状或微观尺度下制备的，形貌多为球状，且合成方法多为电弧熔化法，碳热冲击法，熔融纺丝法或气溶胶喷雾热解法等，这些方法通常需要高温高压的苛刻实验条件以及昂贵的仪器设备，不适合后期规模化生产。特别是对于多功能型多元合金催化剂，形貌可控合成仍然具有非常大的挑战性。
发明内容
为了解决现有技术问题，本发明提供了一种星形的铂铁镍铜钌多元合金固溶体多功能电催化材料及其制备方法。本发明采用简单的湿化学还原法，在低温(＜250℃)常压的条件下快速合成了负载于碳纳米管上的呈星型的PtFeNiCuRu多元合金固溶体纳米催化剂，表现出优异的HER(1M KOH，10mA·cm-2电流密度下，η＝20mV)、OER(1M KOH，10mA·cm-2电流密度下，η＝259mV)和ORR(0.1M HClO4，η＝0.87V)电催化性能和较好的稳定性，实现了具有规则形貌的多元合金固溶体多功能型纳米催化剂的合成。
本发明的另一目的在于提供上述电催化材料的应用。所述电催化材料用于锌空电池、电解水制氢和/或氢氧燃料电池。本发明的电催化材料用于锌空电池中，表现出150mW的大功率电流密度及优良的充放电循环稳定性。此外，所述电催化材料优异的碱性HER、OER性能使其能够应用于电化学全解水生产氢气和氧气，大大降低了水解过电位，减少了生产成本；且其优异的酸性ORR性能使其能够应用于氢氧燃料电池中。
为实现上述目的，本发明采用的技术方案为：
一种星形的铂铁镍铜钌多元合金固溶体多功能电催化材料的制备方法，包括以下步骤：
1)将十六烷基氯化铵(CTAC)分散于油胺(OAM)中，获得分散液；将乙酰丙酮铂、乙酰丙酮铁、乙酰丙酮钌、乙酰丙酮镍、乙酰丙酮铜、碳纳米管(CNT)、葡萄糖以及Mo(CO)6分散于分散液中，获得混合分散液；
2)将混合分散液进行加热处理，获得星形的铂铁镍铜钌多元合金固溶体多功能电催化材料；所述加热处理的温度为200～230℃。
所述十六烷基氯化铵与油胺的质量体积比为(80～120)mg：25mL。
所述乙酰丙酮铂、乙酰丙酮铁、乙酰丙酮钌、乙酰丙酮镍、乙酰丙酮铜、碳纳米管(CNT)、葡萄糖以及Mo(CO)6的质量比为(13～17)：(6～8)：(3～5)：(8～12)：(8～12)：(45～65)：(80～120)：(40～50)。
所述十六烷基氯化铵与乙酰丙酮铂的质量比为(80～120)：(13～17)。
步骤2)中所述加热处理的时间为2～4h。
步骤1)中所述将十六烷基氯化铵(CTAC)分散于油胺(OAM)中是指通过超声分散。
步骤1)中所述分散于分散液中是指超声分散。超声的时间为2～4h。
步骤2)中加热处理后，进行后续处理；所述后续处理是指冷却后，将反应产物进行离心，用环己烷和乙醇的混合物进行洗涤，再次离心，用乙酸醇溶液加热浸泡，乙醇洗涤，干燥。
环己烷和乙醇的体积比为1:(1～2)；
所述乙酸醇溶液为0.4～0.6M的乙酸醇溶液；加热浸泡的温度为40～60℃，加热浸泡的时间为3～5小时；所述干燥为在30～40℃下真空干燥。
本发明中CTAC可促进催化剂高指数晶面的形成。油胺作为溶剂和还原剂之一。Ru的引入调控了催化剂的形貌和电子结构。
本发明的有益效果是：
1、本发明提供的一种星形的铂铁镍铜钌多元合金固溶体多功能电催化材料是以碳纳米管为导电基底的，实现了多元合金纳米颗粒在基底上的均匀分散以及提高了其导电性，减少了实验步骤。
2、本发明的铂铁镍铜钌多元合金固溶体材料是多功能纳米催化剂，表现出优异的HER(1M KOH，10mA·cm-2电流密度下，η＝20mV)、OER(1M KOH，10mA·cm-2电流密度下，η＝259mV)和ORR(0.1M HClO4，η＝0.87V)电催化性能和较好的稳定性，并将其应用于锌空电池上达到150mW的大功率密度，实现了具有规则形貌的多元合金固溶体多功能型纳米催化剂的合成。
3、本发明的催化材料中少量的钌造成的压缩效应导致催化材料的d带中心下移，使其偏离费米能级，削弱了催化剂与表面吸附剂的相互作用，促进了物质转移和化学反应动力学，从而使得合金催化剂的电催化活性显著提高。
4、本发明提供了一种酸泡加热去除催化剂表面油胺的方法，简单快捷。
附图说明
图1是本发明实施例1制备的铂铁镍铜钌多元合金固溶体催化剂(PtFeNiCuRu/CNT)及对比例1制备的铂铁镍铜多元合金固溶体催化剂(PtFeNiCu/CNT)的XRD谱图；
图2是实施例1制备的PtFeNiCuRu/CNT催化剂的透射电镜图像(浅色条状为碳纳米管CNT，深色颗粒为PtFeNiCuRu多元合金纳米颗粒)；
图3是对比例1制备的PtFeNiCu/CNT催化剂的透射电镜图像(浅色条状为碳纳米管CNT，深色颗粒为PtFeNiCu多元合金纳米颗粒)；
图4是实施例1制备的PtFeNiCuRu/CNT催化剂及对比例1制备的PtFeNiCu/CNT催化剂在1M KOH测得的HER性能；
图5是实施例1制备的PtFeNiCuRu/CNT催化剂及对比例1制备的PtFeNiCu/CNT催化剂在1M KOH测得的HER阻抗图谱；
图6是实施例1制备的PtFeNiCuRu/CNT催化剂及对比例1制备的PtFeNiCu/CNT催化剂在1M KOH测得的OER性能；
图7是实施例1制备的PtFeNiCuRu/CNT催化剂及对比例1制备的PtFeNiCu/CNT催化剂在1M KOH测得的OER阻抗图谱；
图8是实施例1制备的PtFeNiCuRu/CNT催化剂及对比例1制备的PtFeNiCu/CNT催化剂在0.1M HClO4测得的ORR性能。
具体实施方式
下面结合具体实施例对本发明作进一步详细的说明，但本发明的实施方式不限于此。
实施例1：铂铁镍铜钌多元合金固溶体催化剂PtFeNiCuRu/CNT
(1)将100mg十六烷基氯化铵(CTAC)溶于25mL油胺(OAM)中，超声处理30mins，得到分散液Ⅰ；
(2)称取乙酰丙酮铂15mg、乙酰丙酮铁6.7mg、乙酰丙酮钌3.8mg、乙酰丙酮镍9.8mg、乙酰丙酮铜10mg、碳纳米管(CNT)56.6mg、葡萄糖100mg以及Mo(CO)6 45mg，一同加入装有分散液Ⅰ容器中，超声3h，得到分散液Ⅱ；
(3)将分散液Ⅱ移入油浴锅中加热搅拌，油浴温度为220℃，加热搅拌时间为2小时；
(4)将步骤(3)反应产物取出冷却后，用环己烷/乙醇(环己烷和乙醇的体积比为1:1)离心收集干燥，再用0.5M的乙酸醇溶液在45℃下酸泡加热4小时，再用乙醇洗涤几次，在35℃下真空干燥，得到星形的铂铁镍铜钌多元合金固溶体材料PtFeNiCuRu/CNT。
本实施例制备的材料中金属元素的原子比：Pt37％，Fe6％，Ni22％，Cu34％，Ru1％。
对比例1：铂铁镍铜多元合金固溶体催化剂PtFeNiCu/CNT
(1)将90mg十六烷基氯化铵(CTAC)溶于22mL油胺(OAM)中，超声处理30mins，得到分散液Ⅰ；
(2)称取乙酰丙酮铂15mg、乙酰丙酮铁6.7mg、乙酰丙酮镍9.8mg、乙酰丙酮铜10mg、碳纳米管(CNT)52.7mg、葡萄糖100mg以及Mo(CO)6 45mg，一同加入装有分散液Ⅰ的容器中，超声3h，得到分散液Ⅱ；
(3)将分散液Ⅱ移入油浴锅中加热搅拌，油浴温度为220℃，加热搅拌时间为2小时。
(4)将步骤(3)反应产物取出冷却后，通过离心收集黑色产物，再加入环己烷和乙醇混合物洗涤两到三次，环己烷和乙醇的体积比为1:1，离心收集干燥，再用0.5M的乙酸醇溶液在45℃下酸泡加热4小时，再用乙醇洗涤几次，在35℃下真空干燥，得到铂铁镍铜多元合金固溶体材料PtFeNiCu/CNT。
结构表征和性能测试：
图1是本发明实施例1制备的铂铁镍铜钌多元合金固溶体催化剂(PtFeNiCuRu/CNT)及对比例1制备的铂铁镍铜多元合金固溶体催化剂(PtFeNiCu/CNT)的XRD谱图；其中PtFeNiCuRu对应实施例1，PtFeNiCu对应对比例1。如图1，实施例1制备的PtFeNiCuRu/CNT的金属特征衍射峰主要位于41.87°、48.40°、70.59°和85.19°处，与金属单质标准卡片对比，多元金属固溶体催化剂的衍射峰位于金属单质衍射峰位置之间，说明了合金固溶体的成功合成；且对比例1制备的PtFeNiCu/CNT的金属特征衍射峰也位于金属单质衍射峰位置之间，再次说明本发明所提供的合金催化剂制备方法的有效性。
图2是实施例1制备的PtFeNiCuRu/CNT催化剂的透射电镜图像，左右两幅图为不同放大倍数的TEM图。如图2，实施例1制备的PtFeNiCuRu多元合金纳米颗粒均匀分散在碳纳米管上，合金颗粒整体上呈现星状，对角线长度约为38.5nm。
图3是对比例1制备的PtFeNiCu/CNT催化剂的透射电镜图像，左右两幅图为不同放大倍数的图。如图3，对比例1制备的PtFeNiCu多元合金纳米颗粒分散在碳纳米管上，合金颗粒整体上呈现立方状，大小约为11.5nm。
图4是实施例1制备的PtFeNiCuRu/CNT催化剂及对比例1制备的PtFeNiCu/CNT催化剂在1M KOH测得的HER性能；其中PtFeNiCuRu对应实施例1，PtFeNiCu对应对比例1。如图4，实施例1制备的PtFeNiCuRu多元合金纳米颗粒表现出优秀的HER性能，在1M KOH中，10mA/cm2电流密度时，过电位仅20mV，小于商业Pt/C(40mV)和PtFeNiCu催化剂(51mV)。Ru的引入使得PtFeNiCuRu/CNT的催化性能显著提高，且相对于商业Pt/C，其催化剂极大地降低了Pt的用量和催化剂的成本。
图5是实施例1制备的PtFeNiCuRu/CNT催化剂及对比例1制备的PtFeNiCu/CNT催化剂在1M KOH测得的HER阻抗图谱；其中PtFeNiCuRu对应实施例1，PtFeNiCu对应对比例1。如图5，实施例1制备的PtFeNiCuRu多元合金纳米颗粒表现出最小的HER阻抗半径，远小于Pt/C和PtFeNiCu催化剂，说明其较后两者具有更小的电阻和更快的HER反应动力学。
图6是实施例1制备的PtFeNiCuRu/CNT催化剂及对比例1制备的PtFeNiCu/CNT催化剂在1M KOH测得的OER性能；其中PtFeNiCuRu对应实施例1，PtFeNiCu对应对比例1。如图6，实施例1制备的PtFeNiCuRu多元合金纳米颗粒表现出优秀的OER性能，在1M KOH中，10mA/cm2电流密度时，过电位仅259mV，小于RuO2(275mV)和PtFeNiCu催化剂(416mV)，催化性能显著提高。
图7是实施例1制备的PtFeNiCuRu/CNT催化剂及对比例1制备的PtFeNiCu/CNT催化剂在1M KOH测得的OER阻抗图谱；其中PtFeNiCuRu对应实施例1，PtFeNiCu对应对比例1。如图7，实施例1制备的PtFeNiCuRu多元合金纳米颗粒表现出最小的OER阻抗半径，远小于Pt/C和PtFeNiCu催化剂，说明其较后两者具有更小的电阻和更快的OER反应动力学。
图8是实施例1制备的PtFeNiCuRu/CNT催化剂及对比例1制备的PtFeNiCu/CNT催化剂在0.1M HClO4测得的ORR性能；其中PtFeNiCuRu对应实施例1，PtFeNiCu对应对比例1。如图8，实施例1制备的PtFeNiCuRu多元合金纳米颗粒表现出优秀的ORR性能，在0.1M HClO4中，半波电位为0.87V，极限扩散电流为5.6mA·cm-2，显著优于Pt/C(0.85V,5mA·cm-2)和PtFeNiCu(0.83V,4.5mA·cm-2)。
Claims (7)
1.一种星形的铂铁镍铜钌钼高熵合金固溶体多功能电催化材料的制备方法，其特征在于：包括以下步骤：1)将十六烷基氯化铵分散于油胺中，获得分散液；将乙酰丙酮铂、乙酰丙酮铁、乙酰丙酮钌、乙酰丙酮镍、乙酰丙酮铜、碳纳米管、葡萄糖以及Mo(CO)6分散于分散液中，获得混合分散液；2)将混合分散液进行加热处理，获得星形的铂铁镍铜钌钼高熵合金固溶体多功能电催化材料；所述加热处理的温度为200～230℃；
所述十六烷基氯化铵与油胺的质量体积比为(80～120)mg：25mL；所述乙酰丙酮铂、乙酰丙酮铁、乙酰丙酮钌、乙酰丙酮镍、乙酰丙酮铜、碳纳米管、葡萄糖以及Mo(CO)6的质量比为(13～17)：(6～8)：(3～5)：(8～12)：(8～12)：(45～65)：(80～120)：(40～50)；所述十六烷基氯化铵与乙酰丙酮铂的质量比为(80～120)：(13～17)。
2.根据权利要求1所述星形的铂铁镍铜钌钼高熵合金固溶体多功能电催化材料的制备方法，其特征在于：步骤2)中所述加热处理的时间为2～4h。
3.根据权利要求1所述星形的铂铁镍铜钌钼高熵合金固溶体多功能电催化材料的制备方法，其特征在于：步骤2)中加热处理后，进行后续处理；所述后续处理是指冷却后，将反应产物进行离心，用环己烷和乙醇的混合物进行洗涤，再次离心，用乙酸醇溶液加热浸泡，乙醇洗涤，干燥。
4.根据权利要求3所述星形的铂铁镍铜钌钼高熵合金固溶体多功能电催化材料的制备方法，其特征在于：所述环己烷和乙醇的体积比为1:(1～2)；
所述乙酸醇溶液为0.4～0.6M的乙酸醇溶液；加热浸泡的温度为40～60℃，加热浸泡的时间为3～5小时；所述干燥为在30～40℃下真空干燥。
5.一种由权利要求1～4任一项所述制备方法得到的星形的铂铁镍铜钌钼高熵合金固溶体多功能电催化材料。
6.根据权利要求5所述星形的铂铁镍铜钌钼高熵合金固溶体多功能电催化材料，其特征在于：所述多功能电催化材料中合金颗粒整体上呈现星状。
7.根据权利要求5或6所述星形的铂铁镍铜钌钼高熵合金固溶体多功能电催化材料的应用，其特征在于：所述星形的铂铁镍铜钌钼高熵合金固溶体多功能电催化材料用于锌空电池、电解水制氢和/或氢氧燃料电池。
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