CN113774422A - 一种应用于电解水的PdCuFeCoNi高熵合金纳米颗粒催化剂的制备方法 - Google Patents
一种应用于电解水的PdCuFeCoNi高熵合金纳米颗粒催化剂的制备方法 Download PDFInfo
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Abstract
本发明公开了一种电解水催化剂的制备方法，制备高熵合金纳米颗粒负载炭黑XC‑72用于催化电解水，属于纳米材料合成领域。合成路线主要包括：在油胺溶剂加入还原金属盐，利用表面活性剂阻止高熵合金纳米颗粒团聚，控制其形成特定形貌；配制洗液清洗合金表面油胺及表面活性剂，获得高分散、粒径均一的高熵合金纳米颗粒；高熵合金颗粒负载炭黑XC‑72得到其电解水催化剂，该催化剂在全pH下均表现出优异的析氢和析氧性能，是一种高效的电解水催化剂。本发明方法制备方法简单、安全，所得的高熵合金纳米催化剂是一种理想的电解水催化剂。
Description
技术领域
本发明涉及合金纳米颗粒催化剂的合成以及新型电化学能源材料技术领域，具体涉及高熵合金电催化剂的合成及电解水方面的应用。
背景技术
氢能作为一种高效、环保的绿色能源，受到了广泛关注。氢气传统的制备方法是电解水的过程，但是常见的商业铂碳催化剂成本高、稳定性差，限制了其发展。现有的非铂基贵金属，如钯(Pd)、钌(Ru)，过渡金属如铁(Fe)、钴(Co)、镍(Ni)等同样具有一定的电解水制氢的催化性能，但性能及其催化稳定性方面均需要进一步提高。因此，开发高效、低成本的电解水催化剂具有重要意义。
合金通常指两种及两种以上金属通过一定方法进行结合，具有优于金属单质的性质。高熵合金通常至少包含5种元素，各元素原子百分率在5%~35%。合金纳米颗粒具有纳米级范围的一维尺寸，表现出体积效应、表面效应、量子尺寸效应等特性，可以改变其理化性质；合金纳米颗粒在催化、电化学、光学等方面表现出与纯金属纳米颗粒不同的性质，但是纳米级的合金纳米颗粒容易团聚，对其催化性能具有一定的限制作用。
传统电解水的过程涉及在阴极发生氢析出的电化学反应，阳极涉及氧气析出的电化学反应。然而阴极电极反应动力学缓慢，成为了电解水过程的关键步骤，设计高效的双功能催化剂是解决问题的关键。
发明内容
本发明主要提供了一种非铂基金属制备高熵合金纳米颗粒催化剂的制备方法，主要用于电解水过程。
本发明是通过以下技术方案实现的，具体包括以下几个步骤：
S1：按比例称取乙酰丙酮钯、乙酰丙酮铜、乙酰丙酮铁、乙酰丙酮钴、乙酰丙酮镍将Pd、Cu、Fe、Co、Ni等五种金属盐在油胺进行混合。
S2：将含表面活性剂的油胺与金属盐混合物混合，需超声分散，保证其混合均匀，超声1h。
S3：表面活性剂对合金纳米颗粒进行保护和修饰，阻止高熵合金纳米颗粒团聚。
S4：将上述混合液进行加热搅拌，获得一种由5种金属组成的高分散粒径均一的高熵合金纳米颗粒。
S5：醇与烷烃的混合洗液清洗合金表面油胺及表面活性剂，高熵合金颗粒负载载体，获得高活性的电解水催化剂。
作为进一步优选方案，所述步骤S1具体包括：金属盐可以为取用钯盐、铜盐、铁盐、钴盐、镍盐于圆底烧瓶，该金属盐包括硝酸盐、醋酸盐、乙酰丙酮盐、氯化盐等。
作为进一步优选方案，所述步骤S2具体包括：表面活性剂可包括聚乙烯吡咯烷酮（PVP）、曲拉通（Triton X-114 ）、十六烷基三甲基溴化铵（CTAB）、聚乙二醇等，且需在油胺溶液中超声分散0.1-2 h。
作为进一步优选方案，所述步骤S3具体包括：将含表面活性剂的油胺与金属盐混合物混合，需超声分散0.5-10 h，保证其混合均匀。
作为进一步优选方案，所述步骤S4具体包括：将上述混合液进行加热搅拌，搅拌速度在200-1000rpm，温度控制在150-250 h，并保温0.5-8h。
作为进一步优选方案，所述步骤S5具体包括：洗液分散剂可以为醇类可以为甲醇、乙醇等，烷烃可以是正己烷、环己烷等。混合洗液其混合比例从1:10 - 10:1。合金总质量与碳载体的质量比应为1%~50%，碳材料可以为炭黑XC-72、石墨烯、纳米管，但不局限于此。
本发明合成了一种电解水催化剂，其不仅可以催化阴极的氢气析出反应（HER），同时也可以提高阳极的氧气析出（OER）反应速率。
再一方面，本发明提供了一种非铂基金属制备高熵合金纳米颗粒催化剂的制备方法。
综上所述，与现有研究相比，本发明的优点在于：用一种简单易得的制备方法将多种过渡金属盐与钯组合制备高效长稳定的高熵合金纳米颗粒电解水催化剂，不仅较低了催化剂成本，同时也提升了其使用寿命。
探讨了不同表面活性剂在合金形成过程中的作用，提高了其催化性能的稳定性及其寿命。
将高熵合金分散在多孔碳材料载体上，具有更稳定的结构和较大的比表面积，有利于更多催化活性位点暴露。
五种金属形成的高熵合金具有优于单质金属的优良性能，金属与金属之间、合金与碳材料之间的协同效应有利于电解水的反应速率提升。
附图说明
图1为高熵合金PdCuFeCoNi在不同放大倍数下的透射电镜（TEM）分析图。
图2为制备的高熵合金PdCuFeCoNi的X射线衍射图谱。
图3中，（a）为高熵合金PdCuFeCoNi与商业Pt/C在0.5M H2SO4中进行的10mV/s的析氢测试曲线。（b）为高熵合金PdCuFeCoNi与商业Pt/C在0.5M PBS缓冲溶液中进行的10mV/s的析氢测试曲线。（c）为高熵合金PdCuFeCoNi与商业Pt/C在1M KOH溶液中进行的10mV/s的线性析氢测试曲线。（d）为高熵合金PdCuFeCoNi与商业RuO2在1M KOH中以1600rpm进行的10mV/s析氧测试曲线。
具体实施方式
下面结合实例对本发明进一步说明，但本发明并不限于以下实施例。
实施例1
将曲拉通与油胺进行混合，超声30min后得到透明油状混合液。称取乙酰丙酮钯、乙酰丙酮铜、乙酰丙酮铁、乙酰丙酮钴、乙酰丙酮镍于50mL的圆底烧瓶中。将上述混合液倒入圆
待混合液降至常温，转移至50mL离心管，加30ml无水乙醇震荡均匀后，以8000rpm的转速对其进行离心，取每次的黑色沉淀继续用乙醇离心3次。配制乙醇与正己烷的混合液，优选体积比为1：1、1：2的混合液对黑色沉淀进行离心洗涤1次。将得到的黑色沉淀在正己烷中进行超声分散，得到黑色的高熵合金溶液PdCuFeCoNi-Triton X-100。
实施例2
将聚乙烯吡咯烷酮（PVP）与油胺进行混合，超声30min后得到透明油状混合液。称取乙酰丙酮钯、乙酰丙酮铜、乙酰丙酮铁、乙酰丙酮钴、乙酰丙酮镍于50mL的圆底烧瓶中。将上述混合液倒入圆底烧瓶进行超混合，超声1h。将混合液加热至200oC，待温度稳定后，保温2h。待混合液降至常温，转移至50mL离心管，加30ml无水乙醇震荡均匀后，以8000rpm的转速对其进行离心，取每次的黑色沉淀继续用乙醇离心3次。配制乙醇与正己烷的混合液，优选体积比为1：1、1：2的混合液对黑色沉淀进行离心洗涤1次。将得到的黑色沉淀在正己烷中进行超声分散，得到黑色的高熵合金溶液PdCuFeCoNi-PVP。
实施例3
取5mL黑色的高熵合金催化剂溶液，加入炭黑XC-72，将混合液超声搅拌各30min，重复两次得到催化剂溶液。工作电极的制备：取5mL催化剂溶液与10mg炭黑XC-72进行负载。取7uL催化剂涂覆在面积为0.07cm2的玻碳电极上，待表面干燥后，滴加2uL质量分数为20%Nafion的乙醇溶液，待其在空气中自然干燥。将工作电极置于电解液中进行析氢或析氧测试，线性伏安曲线的扫速一般为10mV/s。
如图1所示，得到的高熵合金是5-8nm的球状颗粒，在高分辨的TEM图像中可以看到清晰的晶格条纹。图2所示的XRD衍射峰，对比标准PDF卡片，相应单质金属特征峰都发生了相应的偏移，居于各标准卡片的中间，说明形成了合金相。在图3的电化学性能测试中，在10mA·cm-2的电流密度下，其酸性析氢电位可以达到-0.021V，与商业Pt/C相仿。同时可以看出，高熵合金催化剂在碱、中性下的析氢反应中具有一定电化学性能，接近商业Pt/C。同时其在碱性条件下也具有与商业RuO2相似的电化学析氧性能。
以上实施例为本发明具有代表性的工作，显然不能代表完整的专利保护范围。任何相似的实验原理、实验操作和药品更换均是对本发明的等价替换，均属本发明保护范围之内。
Claims (7)
1.一种应用于电解水的PdCuFeCoNi高熵合金纳米颗粒催化剂的制备方法，其特征在于：(1)将Pd、Cu、Fe、Co、Ni等五种还原性金属盐在油胺中进行混合加热，在安全、可控的温度下进行反应;(2)将含表面活性剂的油胺与金属盐混合物混合，需超声分散，保证其混合均匀;(3)表面活性剂对合金纳米颗粒进行保护和修饰，阻止高熵合金纳米颗粒团聚;(4)将上述混合液进行加热搅拌，获得一种由5种金属组成的高分散粒径均一的高熵合金纳米颗粒;(5)醇与烷烃的混合洗液清洗合金表面油胺及表面活性剂，高熵合金颗粒负载于载体上得到其电解水催化剂。
2.根据权利要求书所述得合金制备过程，其特征在于：步骤（1）中取用钯盐、铜盐、铁盐、钴盐、镍盐于圆底烧瓶，该金属盐包括硝酸盐、醋酸盐、乙酰丙酮盐、氯化盐等，但不局限于此。
3.根据权利要求书所述得合金制备过程，其特征在于：步骤（2）中表面活性剂可包括聚乙烯吡咯烷酮（PVP）、曲拉通（Triton X-114 ）、十六烷基三甲基溴化铵（CTAB）、聚乙二醇等，且需在油胺溶液中超声分散0.1-2 h。
4.根据权利要求书所述得合金制备过程，其特征在于：步骤（3）中将含表面活性剂的油胺与金属盐混合物混合，需超声分散0.5-10 h，保证其混合均匀。
5.根据权利要求书所述得合金制备过程，其特征在于：步骤（4）中将上述混合液进行加热搅拌，搅拌速度在200-1000rpm，温度控制在150-250 oC，并保温0.5-8h。
6.根据权利要求书所述得合金制备过程，其特征在于：步骤（5）中洗液分散剂可以为醇类可以为甲醇、乙醇等，烷烃可以是正己烷、环己烷等,但不局限于此，混合洗液其混合比例从1:10 - 10:1。
7.根据权利要求书所述得合金制备过程，其特征在于：步骤（5）中合金总质量与碳载体的质量比应为1%~50%，碳材料可以为炭黑XC-72、石墨烯、纳米管，但不局限于此。
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