Department of Chemistry, Brown University , Providence, Rhode Island 02912, United States.
Materials Physics and Application Division, Los Alamos National Laboratory , Los Alamos, New Mexico 87545, United States.
J Am Chem Soc. 2018 Feb 28;140(8):2926-2932. doi: 10.1021/jacs.7b12829. Epub 2018 Feb 15.
We report in this article a detailed study on how to stabilize a first-row transition metal (M) in an intermetallic L1-MPt alloy nanoparticle (NP) structure and how to surround the L1-MPt with an atomic layer of Pt to enhance the electrocatalysis of Pt for oxygen reduction reaction (ORR) in fuel cell operation conditions. Using 8 nm FePt NPs as an example, we demonstrate that Fe can be stabilized more efficiently in a core/shell structured L1-FePt/Pt with a 5 Å Pt shell. The presence of Fe in the alloy core induces the desired compression of the thin Pt shell, especially the two atomic layers of Pt shell, further improving the ORR catalysis. This leads to much enhanced Pt catalysis for ORR in 0.1 M HClO solution (at both room temperature and 60 °C) and in the membrane electrode assembly (MEA) at 80 °C. The L1-FePt/Pt catalyst has a mass activity of 0.7 A/mg from the half-cell ORR test and shows no obvious mass activity loss after 30 000 potential cycles between 0.6 and 0.95 V at 80 °C in the MEA, meeting the DOE 2020 target (<40% loss in mass activity). We are extending the concept and preparing other L1-MPt/Pt NPs, such as L1-CoPt/Pt NPs, with reduced NP size as a highly efficient ORR catalyst for automotive fuel cell applications.
本文详细研究了如何稳定第一过渡金属(M)在金属间 L1-MPt 合金纳米颗粒(NP)结构中,以及如何用一层原子厚的 Pt 包围 L1-MPt,以增强燃料电池操作条件下 Pt 对氧还原反应(ORR)的电催化作用。我们以 8nm 的 FePt NPs 为例,证明 Fe 可以更有效地稳定在具有 5Å Pt 壳的核/壳结构 L1-FePt/Pt 中。合金核中 Fe 的存在诱导所需的薄 Pt 壳的压缩,特别是 Pt 壳的两个原子层,进一步提高了 ORR 催化性能。这导致在 0.1 M HClO 溶液中(在室温及 60°C 下)以及在 80°C 的膜电极组件(MEA)中,Pt 对 ORR 的催化作用大大增强。L1-FePt/Pt 催化剂在半电池 ORR 测试中的质量活性为 0.7 A/mg,在 MEA 中在 80°C 下在 0.6 至 0.95V 之间进行 30000 次电位循环后,其质量活性没有明显损失,达到了 DOE 2020 目标(<40%的质量活性损失)。我们正在扩展这一概念并制备其他 L1-MPt/Pt NPs,例如 L1-CoPt/Pt NPs,其 NP 尺寸更小,是用于汽车燃料电池的高效 ORR 催化剂。