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Advanced Pt-Based Core–Shell Electrocatalysts for Fuel Cell Cathodes
Accounts of Chemical Research ( IF 16.4 ) Pub Date : 2022-04-22 , DOI: 10.1021/acs.accounts.2c00057 Xueru Zhao 1 , Kotaro Sasaki 1
Accounts of Chemical Research ( IF 16.4 ) Pub Date : 2022-04-22 , DOI: 10.1021/acs.accounts.2c00057 Xueru Zhao 1 , Kotaro Sasaki 1
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Proton-exchange membrane fuel cells (PEMFCs) are highly efficient energy storage and conversion devices. Thus, the platinum group metal (PGM)-based catalysts which are the dominant choice for the PEMFCs have received extensive interest during the past couple of decades. However, the drawbacks in the existing PGM-based catalysts (i.e., high cost, slow kinetics, poor stability, etc.) still limit their applications in fuel cells. The Pt-based core–shell catalysts potentially alleviate these issues through the low Pt loading with the associated low cost and the high corrosion resistance and further improve the oxygen reduction reaction’s (ORR’s) activity and stability. This Account focuses on the synthetic strategies, catalytic mechanisms, factors influencing enhanced ORR performance, and applications in PEMFCs for the Pt-based core–shell catalysts. We first highlight the synthetic strategies for Pt-based core–shell catalysts including the galvanic displacement of an underpotentially deposited non-noble metal monolayer, thermal annealing, and dealloying methods, which can be scaled-up to meet the requirements of fuel cell operations. Subsequently, catalytic mechanisms such as the self-healing mechanism in the Pt monolayer on Pd core catalysts, the pinning effect of nitrogen (N) dopants in N-doped PtNi core–shell catalysts, and the ligand effect of the ordered intermetallic structure in L10-Pt/CoPt core–shell catalysts and their synergistic effects in N-doped L10-PtNi catalysts are described in detail. The core–shell structure in the Pt-based catalysts have two main effects for enhanced ORR performance: (i) the interaction between Pt shells and core substrates can tune the electronic state of the surface Pt, thus boosting the ORR activity and stability, and (ii) the outer Pt shell with modest thickness can enhance the oxidation and dissolution resistance of the core, resulting in improved durability. We then review the recent attempts to optimize the ORR performance of the Pt-based core–shell catalysts by considering the shape, composition, surface orientation, and shell thickness. The factors influencing the ORR performance can be grouped into two categories: the effect of the core and the effect of the shell. In the former, PtM core–shell catalysts which use different non-PGM element cores (M) are summarized, and in the latter, Pt-based core–shell catalysts with different shell structures and compositions are described. The modifications of the core and/or shell structure can not only optimize the intermediate-binding energetics on the Pt surface through tuning the strain of the surface Pt, which increases the intrinsic activity and stability, but also offer a significantly decreased catalyst cost. Finally, we discuss the membrane electrode assembly performance of Pt-based core–shell catalysts in fuel cell cathodes and evaluate their potential in real PEMFCs for light-duty and heavy-duty vehicle applications. Even though some challenges to the activity and lifetime in the fuel cells remain, the Pt-based core–shell catalysts are expected to be promising for many practical PEMFC applications.
中文翻译：
用于燃料电池阴极的先进铂基核壳电催化剂
质子交换膜燃料电池 (PEMFC) 是一种高效的能量存储和转换装置。因此，作为 PEMFC 的主要选择的铂族金属 (PGM) 基催化剂在过去的几十年中受到了广泛的关注。然而，现有的基于PGM的催化剂的缺点（即成本高、动力学慢、稳定性差等）仍然限制了它们在燃料电池中的应用。Pt 基核壳催化剂可能通过低 Pt 负载、相关的低成本和高耐腐蚀性来缓解这些问题，并进一步提高氧还原反应 (ORR) 的活性和稳定性。本报告侧重于 Pt 基核壳催化剂的合成策略、催化机制、影响增强 ORR 性能的因素以及在 PEMFC 中的应用。我们首先强调了 Pt 基核壳催化剂的合成策略，包括电置换低电位沉积的非贵金属单层、热退火和脱合金方法，这些方法可以扩大规模以满足燃料电池操作的要求。随后，Pd 核催化剂上 Pt 单分子层的自愈机制、N 掺杂 PtNi 核壳催化剂中氮 (N) 掺杂剂的钉扎效应以及 L1 中有序金属间化合物结构的配体效应等催化机制0 -Pt/CoPt核壳催化剂及其在N掺杂L1中的协同效应0-PtNi 催化剂被详细描述。Pt 基催化剂中的核壳结构对提高 ORR 性能有两个主要影响：（i）Pt 壳层和核底物之间的相互作用可以调节表面 Pt 的电子态，从而提高 ORR 活性和稳定性，以及(ii) 适度厚度的 Pt 外壳可以增强核的抗氧化和抗溶解性，从而提高耐久性。然后，我们回顾了最近通过考虑形状、组成、表面取向和壳厚度来优化 Pt 基核壳催化剂的 ORR 性能的尝试。影响 ORR 性能的因素可以分为两类：核的影响和壳的影响。在前者中，总结了使用不同非PGM元素核（M）的PtM核壳催化剂，并在后者中描述了具有不同壳结构和组成的Pt基核壳催化剂。核和/或壳结构的修饰不仅可以通过调整表面Pt的应变来优化Pt表面的中间结合能，从而提高内在活性和稳定性，而且还可以显着降低催化剂成本。最后，我们讨论了 Pt 基核壳催化剂在燃料电池阴极中的膜电极组装性能，并评估了它们在用于轻型和重型车辆应用的实际 PEMFC 中的潜力。尽管燃料电池的活性和寿命仍然存在一些挑战，
更新日期：2022-04-22
中文翻译：
用于燃料电池阴极的先进铂基核壳电催化剂
质子交换膜燃料电池 (PEMFC) 是一种高效的能量存储和转换装置。因此，作为 PEMFC 的主要选择的铂族金属 (PGM) 基催化剂在过去的几十年中受到了广泛的关注。然而，现有的基于PGM的催化剂的缺点（即成本高、动力学慢、稳定性差等）仍然限制了它们在燃料电池中的应用。Pt 基核壳催化剂可能通过低 Pt 负载、相关的低成本和高耐腐蚀性来缓解这些问题，并进一步提高氧还原反应 (ORR) 的活性和稳定性。本报告侧重于 Pt 基核壳催化剂的合成策略、催化机制、影响增强 ORR 性能的因素以及在 PEMFC 中的应用。我们首先强调了 Pt 基核壳催化剂的合成策略，包括电置换低电位沉积的非贵金属单层、热退火和脱合金方法，这些方法可以扩大规模以满足燃料电池操作的要求。随后，Pd 核催化剂上 Pt 单分子层的自愈机制、N 掺杂 PtNi 核壳催化剂中氮 (N) 掺杂剂的钉扎效应以及 L1 中有序金属间化合物结构的配体效应等催化机制0 -Pt/CoPt核壳催化剂及其在N掺杂L1中的协同效应0-PtNi 催化剂被详细描述。Pt 基催化剂中的核壳结构对提高 ORR 性能有两个主要影响：（i）Pt 壳层和核底物之间的相互作用可以调节表面 Pt 的电子态，从而提高 ORR 活性和稳定性，以及(ii) 适度厚度的 Pt 外壳可以增强核的抗氧化和抗溶解性，从而提高耐久性。然后，我们回顾了最近通过考虑形状、组成、表面取向和壳厚度来优化 Pt 基核壳催化剂的 ORR 性能的尝试。影响 ORR 性能的因素可以分为两类：核的影响和壳的影响。在前者中，总结了使用不同非PGM元素核（M）的PtM核壳催化剂，并在后者中描述了具有不同壳结构和组成的Pt基核壳催化剂。核和/或壳结构的修饰不仅可以通过调整表面Pt的应变来优化Pt表面的中间结合能，从而提高内在活性和稳定性，而且还可以显着降低催化剂成本。最后，我们讨论了 Pt 基核壳催化剂在燃料电池阴极中的膜电极组装性能，并评估了它们在用于轻型和重型车辆应用的实际 PEMFC 中的潜力。尽管燃料电池的活性和寿命仍然存在一些挑战，
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