Inflating hollow nanocrystals through a repeated Kirkendall cavitation process

He Tianou,Zhenming Cao,Xiaolong Yang,Weicong Wang,Zhiwei Shan,Yadong Yin,Zhao Wang,Qin Kuang,Mingshang Jin

doi:10.1038/s41467-017-01258-0

Abstract

The Kirkendall effect has been recently used to produce hollow nanostructures by taking advantage of the different diffusion rates of species involved in the chemical transformations of nanoscale objects. Here we demonstrate a nanoscale Kirkendall cavitation process that can transform solid palladium nanocrystals into hollow palladium nanocrystals through insertion and extraction of phosphorus. The key to success in producing monometallic hollow nanocrystals is the effective extraction of phosphorus through an oxidation reaction, which promotes the outward diffusion of phosphorus from the compound nanocrystals of palladium phosphide and consequently the inward diffusion of vacancies and their coalescence into larger voids. We further demonstrate that this Kirkendall cavitation process can be repeated a number of times to gradually inflate the hollow metal nanocrystals, producing nanoshells of increased diameters and decreased thicknesses. The resulting thin palladium nanoshells exhibit enhanced catalytic activity and high durability toward formic acid oxidation.

Highlights

The Kirkendall effect has been recently used to produce hollow nanostructures by taking advantage of the different diffusion rates of species involved in the chemical transformations of nanoscale objects
We started with the synthesis of uniform Pd nanocubes using a method that we developed previously[35,36,37], and use these nanocubes to react with trioctylphosphine (TOP) at 250 °C to produce phosphide nanocrystals
Bright-field transmission electron microscopy (TEM) images in Fig. 2a, b show that the original Pd nanocubes with an average edge length of 18 nm were transformed into spherical solid phosphide particles with an average diameter of ~ 20 nm

Summary

Introduction

The Kirkendall effect has been recently used to produce hollow nanostructures by taking advantage of the different diffusion rates of species involved in the chemical transformations of nanoscale objects. We demonstrate that Kirkendall voids can be formed by extracting a species X from solid nanocrystals of a compound MX, allowing the production of monometallic hollow nanocrystals.

Results

Conclusion