Atomic Diffusion Engineered PtSnCu Nanoframes with High‐Index Facets Boost Ethanol Oxidation

• Published in: Advanced materials (Weinheim) Vol. 36; no. 21; pp. e2311731 - n/a
• Main Authors: Tang, Min, Sun, Mingzi, Chen, Wen, Ding, Yutian, Fan, Xiaokun, Wu, Xiaoyu, Fu, Xian‐Zhu, Huang, Bolong, Luo, Shuiping, Luo, Jing‐Li
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 01.05.2024
• Subjects: Acidic oxides; atomic diffusion; Carbon monoxide; Density functional theory; Diffusion; Electroactivity; electrocatalysis; Electrocatalysts; Ethanol; ethanol oxidation; high‐index facets; Liquid fuels; Nanoalloys; nanoframes; Oxidation; ethanol oxidation; high-index facets; atomic diffusion.electrocatalysis; nanoframes
• ISSN: 0935-9648; 1521-4095; 1521-4095
• DOI: 10.1002/adma.202311731

Electrochemical ethanol oxidation is crucial to directly convert a biorenewable liquid fuel with high energy density into electrical energy, but it remains an inefficient reaction even with the best catalysts. To boost ethanol oxidation, developing multimetallic nanoalloy has emerged as one of the most effective strategies, yet faces a challenge in the rational engineering of multimetallic active‐site ensembles at atomic‐level. Herein, starting from typical PtCu nanocrystals, an atomic Sn diffusion strategy is developed to construct well‐defined Pt47Sn12Cu41 octopod nanoframes, which is enclosed by high‐index facets of n (111)‐(111), such as {331} and {221}. Pt47Sn12Cu41 achieves a high mass activity of 3.10 A mg−1Pt and promotes the C‐C bond breaking and oxidation of poisonous CO intermediate, representing a state‐of‐the‐art electrocatalyst toward ethanol oxidation in acidic electrolyte. Density functional theory （DFT） calculations have confirmed that the introduction of Sn improves the electroactivity by uplifting the d‐band center through the s‐p‐d coupling. Meanwhile, the strong binding of ethanol and the reduced energy barrier of CO oxidation guarantee a highly efficient ethanol oxidation process with improved Faradic efficiency of C1 products. This work offers a promising strategy for constructing novel multimetallic nanoalloys tailored by atomic metal sites as the efficient electrocatalysts. Ternary PtSnCu active‐site ensembles with enlarged lattice spacings and high‐index facets are achieved by atomic Sn diffusion into the PtCu octopod nanoframes. Benefiting from the single‐atom Sn tailoring, the Pt47Sn12Cu41 octopod nanoframes exhibit ultrahigh and all‐round superior electrocatalytic performances including activity, selectivity, stability, and anti‐poisoning ability toward the electrochemical ethanol oxidation in acidic electrolyte.