铂基多组分金属间化合物纳米盘的合成及电催化性能研究

为了满足社会发展需求，开发高效清洁的新能源已迫在眉睫。燃料电池因其高效、清洁、可靠性高等优点，成为现阶段最有发展前景的能源转化技术之一，但受限于缓慢的动力学反应过程。因此，开发高效稳定且低成本的 Pt 基催化剂是燃料电池领域和纳米材料领域近二十年来的研究热点。 Pt 基催化剂的主要开发策略包括： 将 Pt 与其他金属合金化调控电子结构，构建不同形状 Pt 纳米晶优化原子的排列方式，以及表面修饰金属氧化物优化电化学反应过程等。 Pt 金属间化合物具有长程有序的原子排布、孤立活性位点和丰富的异原子键，通常表现出优异的催化活性、选择性和稳定性，是目前电催化剂的研究前沿。然而，原子有序化过程动力学能垒高，往往需要高温条件，限制了其结构和功能的调控，采用低温液相法且系统地制备 Pt 基金属间化合物十分困难，目前关于多组分 Pt 基金属间化合物的研究工作仍非常有限。本论文开发了一种简单通用的液相合成法，获得了一系列新颖且原子结构明确的 Pt 基金属间化合物纳米盘，进行了清晰的结构表征，对其生长机理、催化性能和催化机理进行了全面的探究，为多金属纳米催化剂的设计与合成提供了重要参考。主要研究内容概括如下：提出了组分可调的三元 PtSnBi 金属间化合物纳米盘的通用合成方法，获得了 Pt47Sn16Bi37、 Pt45Sn25Bi30 和 Pt45Sn34Bi21 纳米盘，证实了原子结构有序的 PtSnBi金属间化合物纳米盘的生长机理为“络合-还原-有序化”过程。三种元素协同作用促进甲酸氧化反应，三元PtSnBi金属间化合物的电催化性能明显优于二元PtSn和 PtBi。特别的， 特定组分的 Pt45Sn25Bi30 纳米盘表现出 4.39 A mg-1Pt 的高质量活性， 并在 4000 圈电位循环稳定性测试后良好地保持了其结构和 78%的初始活性。理论计算揭示 PtSnBi 金属间化合物的电子效应和几何效应抑制了 CO*的形成，优化了甲酸脱氢步骤，从而促进了甲酸直接氧化。基于 PtBi、 RhBi、 PtSn 和 PtSb 的相同 hcp 晶体结构，通过原子柱上异质元素选择性取代合成了 hcp 结构的 PtRhBiSnSb 高熵金属间化合物（HEI）纳米盘。结构明确的 PtRhBiSnSb HEI 纳米盘中具有本征孤立的 Pt、 Rh、 Bi、 Sn、 Sb 原子位点，五种金属的协同作用使其对碱性条件下的甲醇、乙醇和甘油氧化反应电催化分别表现出 19.53、 15.56 和 7.54 A mg-1Pt+Rh 的高质量活性。理论计算表明，金属 Rh 的引入提高了 PtRhBiSnSb HEI 纳米盘的电子转移效率，从而提高了醇氧化能力。同时， Bi、 Sn 和 Sb 位点的协同保护，使活性位点具备稳定的电子结构和催化性能。将具有孤立 Pt 原子位点的 PtBi 金属间化合物纳米盘作为基底，在其表面上可控生长 Pb 原子，探究多金属且原子结构明确的电催化剂对甲醇氧化反应的协同促进作用。结构明确的 PtBi@6.7%Pb 纳米盘表面镶嵌了 sub-羟基氧化铅原子层，三种元素协同作用使其在碱性甲醇氧化反应中催化质量活性达到 PtBi 纳米盘和商业 Pt/C 的 4.0 和 7.4 倍（30 ℃），并在直接甲醇燃料电池通常的运行温度下（60 ℃）达到 51.07 A mg-1Pt。理论计算显示，表面羟基氧化铅的引入不仅促进了有效电子转移，还抑制了 CO 毒化效应，有效的 p-d 耦合优化了 PtBi@6.7%Pb纳米盘的甲醇氧化反应过程，使其反应能垒降低。

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