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Shape Control of Monodispersed Sub‐5 nm Pd Tetrahedrons and Laciniate Pd Nanourchins by Maneuvering the Dispersed State of Additives for Boosting ORR Performance
Author(s) -
Zhang Huaifang,
Qiu Xiaoyu,
Chen Yifan,
Wang Shangzhi,
Skrabalak Sara E.,
Tang Yawen
Publication year - 2020
Publication title -
small
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 3.785
H-Index - 236
eISSN - 1613-6829
pISSN - 1613-6810
DOI - 10.1002/smll.201906026
Subject(s) - nanocrystal , density functional theory , materials science , catalysis , formic acid , delafossite , tetrahedron , kinetic energy , kinetics , chemical engineering , nanotechnology , crystallography , chemistry , computational chemistry , metallurgy , organic chemistry , oxide , physics , quantum mechanics , engineering
It is a great challenge to simultaneously control the size, morphology, and facets of monodispersed Pd nanocrystals under a sub‐5 nm regime. Meanwhile, quantitative understanding of the thermodynamic and kinetic parameters to maneuver the shape evolution of nanocrystals in a one‐pot system still deserves investigation. Herein, a systematic study of the density functional theory (DFT)‐calculated adsorption energy, thermodynamic factors, and reduction kinetics on Pd growth patterns is reported by combining theory and experiments, with a focus on the dispersed state of additives. As pure models, monodispersed Pd tetrahedrons enclosed by (111) facets with a narrow size distribution of 4.9 ± 1 nm and a high purity approaching 98% can be obtained when using 1,1′‐binaphthalene (C 20 H 14 ) +2NH 3 as additives. Specifically, laciniate Pd nanourchins (Pd LUs) can evolve via anisotropic growth when replacing additive with dose‐consistent 1,1′‐binaphthyl‐2,2′‐diamine (C 20 H 16 N 2 , two NH 2 binding in C 20 H 14 ). Catalytic investigations show that the sub‐5 nm Pd tetrahedrons exhibit higher activity in both the oxygen reduction ( E onset = 1.025 V, E 1/2 = 0.864 V) and formic acid oxidation reaction with respect to the Pd LUs and Pd black, which represents a great step for the development of well‐defined Pd nanocrystals with size in the sub‐5 nm regime as non‐Pt electrocatalysts.