Stable Strain State of Single-Twinned AgPdF Nanoalloys under Formate Oxidation Reaction

Q Tang and LF Guo and T Jin and S Shan and Q Wang and JP Wang and BW Pan and Z Li and YH Chai and FY Chen, SMALL STRUCTURES, 4 (2023).

DOI: 10.1002/sstr.202300110

Surface reconstruction as common phenomenon during catalysis complicates the prediction and modeling on catalytic activity of the nanoalloy, hence developing a stable structure to be resistant to surface restructuring would provide an ideal prototype for substantial and reliable mechanism analysis. Herein, the single-twinned structure in inverse AgPdF catalyst is constructed to enhance the catalytic activity and stability for the formate oxidation reaction (FOR). The single- twinned AgPdF nanoalloy (t-AgPdF) catalyst exhibits an enhanced peak current density of 4.6 A mg(Pd)(-1), a reduced onset potential of 0.44 V, a higher activity retention of 55.7% after 600 cycles, and a longer activity retention time of 55.9 h. Additionally, the t-AgPdF catalyst presents a higher hydrogen generation rate of 1.11 mL mg(Pd)(-1) than that of single-crystalline AgPd nanoalloy (AgPd) catalyst, and density functional theory calculations reveal that t-AgPdF(111) surface exhibits a reduced activation energy of 0.59 eV for formate decomposition reaction. Impressively, the t-AgPdF maintains compressive and tensile strain state along the sigma 3 twin boundaries before and after the FOR, in contrast to AgPd. This is the first time to reveal that the nanotwinned structures contribute inverse t-AgPdF catalysts the catalytic active sites with stable strain state since starting reaction for the FOR.

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