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A Quantitative Analysis of the Reduction Kinetics Involved in the Synthesis of Au@Pd Concave Nanocubes
Author(s) -
Xie Minghao,
Zhou Shan,
Zhu Jiawei,
Lyu Zhiheng,
Chen Ruhui,
Xia Younan
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201904074
Subject(s) - kinetics , metal , nanocrystal , bromide , chemistry , palladium , ascorbic acid , catalysis , materials science , chemical engineering , nanotechnology , inorganic chemistry , organic chemistry , physics , food science , quantum mechanics , engineering
Surface capping has been shown to play a pivotal role in controlling the evolution of metal nanocrystals into different shapes or morphologies. With the synthesis of Au@Pd concave nanocubes as an example, here we demonstrate that the capping agent can also impact the reduction kinetics of a precursor, and thereby its reduction pathway, for the formation of metal nanocrystals with distinct morphologies. A typical synthesis involves the reduction of a Pd II precursor by ascorbic acid at room temperature in the presence of Au nanospheres as seeds, together with the use of hexadecyltrimethylammonium chloride (CTAC) or hexadecyltrimethylammonium bromide (CTAB) as the capping agent. In the case of CTAC, the Pd II precursor prevails as PdCl 4 2− , leading to the formation of Au@Pd concave nanocubes with a rough surface because of the fast reduction kinetics and thus the dominance of solution reduction pathway. When switched to CTAB, the Pd II precursor changes to PdBr 4 2− that features slow reduction kinetics and surface reduction pathway. Accordingly, the Au@Pd concave nanocubes take a smooth surface. This work demonstrates that both reduction kinetics and surface capping play important roles in controlling the morphology of metal nanocrystals and these two roles are often coupled to each other.