Strain in Core–Shell Spinel Nanocrystals Enhances ORR Activity

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2025-05-24 DOI:10.1021/acscatal.5c00896

Jonathan L. Rowell, Aditya Joshi, Haotian Tan, Dasol Yoon, Jason Manassa, Alex Stangel, Colin Bundschu, Yafu Jia, Héctor D. Abruña, Robert Hovden, David A. Muller, Richard D. Robinson

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Abstract

Strain engineering of electrocatalysts has been an extensively studied field in recent years, but there has been limited investigation of strain and ligand effects in the catalysts of heterostructured oxides. Such studies could have significant impacts as the localized changes in the electronic structure of metal oxide shells may induce enhanced catalytic activity, complementing those from the well-studied metallic systems. Here, we developed a colloidal synthesis route to monodisperse core–shell spinel oxide nanocrystals with tunable shell thickness for the oxygen reduction reaction (ORR) in alkaline media. We compare the activity of these heterostructured particles, finding a higher activity for smaller shell thicknesses. The smallest shell thickness aligns with the highest shell strain. The best-performing core–shell sample achieved a half-wave potential of 0.893 V versus RHE in 1.0 M KOH, making it one of the best-reported values for a spinel oxide electrocatalyst for alkaline ORR with a PGM-free catalyst. In addition, this value is within 11 mV of that of the Pt/C reference material. Though a Pt/C reference sample has an overall higher mass activity at 0.9 V vs RHE, when cost is considered, the strained spinel outperforms the Pt/C by over 600-fold at this potential. Our results provide an impetus for exploring the deliberate and controlled use of strain engineering in metal oxides as high-performance, low-cost electrocatalysts.

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核壳尖晶石纳米晶体应变增强ORR活性

电催化剂的应变工程是近年来广泛研究的一个领域，但对异质结构氧化物催化剂的应变和配体效应的研究有限。这些研究可能会产生重大影响，因为金属氧化物壳层电子结构的局部变化可能会诱导催化活性增强，补充那些已经得到充分研究的金属体系。在这里，我们开发了一种胶体合成路线，以单分散的核-壳尖晶石氧化纳米晶体，其壳厚可调，用于碱性介质中的氧还原反应（ORR）。我们比较了这些异质结构粒子的活性，发现壳厚度越小，活性越高。最小的壳厚与最高的壳应变一致。在1.0 M KOH条件下，最佳的核壳样品相对于RHE的半波电位为0.893 V，使其成为无ppg催化剂的尖晶石氧化物电催化剂碱性ORR的最佳报道值之一。此外，该值与Pt/C参考材料的值相差在11mv以内。虽然Pt/C参考样品在0.9 V时比RHE具有更高的总体质量活性，但考虑到成本，应变尖晶石在此电位下的性能优于Pt/C 600倍以上。我们的研究结果为探索应变工程在金属氧化物中作为高性能、低成本电催化剂的有意和可控使用提供了动力。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.