Tailoring electrocatalytic activity of in situ crafted perovskite oxide nanocrystals via size and dopant control

Yeu Wei Harn, Shuang Liang, Shuanglong Liu, Yan Yan, Zewei Wang, Jun Jiang, Jiawei Zhang, Qiong Li, Yanjie He, Zili Li, Lei Zhu, Hai Ping Cheng, Zhiqun Lin

Research output: Contribution to journalArticlepeer-review

22 Scopus citations

Abstract

Perovskite oxides (ABO3) have been widely recognized as a class of promising noble-metal–free electrocatalysts due to their unique compositional flexibility and structural stability. Surprisingly, investigation into their size-dependent electrocatalytic properties, in particular barium titanate (BaTiO3), has been comparatively few and limited in scope. Herein, we report the scrutiny of size- and dopant-dependent oxygen reduction reaction (ORR) activities of an array of judiciously designed pristine BaTiO3 and doped BaTiO3 (i.e., La- and Co-doped) nanoparticles (NPs). Specifically, a robust nanoreactor strategy, based on amphiphilic star-like diblock copolymers, is employed to synthesize a set of hydrophobic polymer-ligated uniform BaTiO3 NPs of different sizes (≤20 nm) and controlled compositions. Quite intriguingly, the ORR activities are found to progressively decrease with the increasing size of BaTiO3 NPs. Notably, La- and Co-doped BaTiO3 NPs display markedly improved ORR performance over the pristine counterpart. This can be attributed to the reduced limiting barrier imposed by the formation of -OOH species during ORR due to enhanced adsorption energy of intermediates and the possibly increased conductivity as a result of change in the electronic states as revealed by our density functional theory–based first-principles calculations. Going beyond BaTiO3 NPs, a variety of other ABO3 NPs with tunable sizes and compositions may be readily accessible by exploiting our amphiphilic star-like diblock copolymer nanoreactor strategy. They could in turn provide a unique platform for both fundamental and practical studies on a suite of physical properties (dielectric, piezoelectric, electrostrictive, catalytic, etc.) contingent upon their dimensions and compositions.

Original languageEnglish
Article numbere2014086118
JournalProceedings of the National Academy of Sciences of the United States of America
Volume118
Issue number25
DOIs
StatePublished - 22 Jun 2021

Bibliographical note

Publisher Copyright:
© 2021 National Academy of Sciences. All rights reserved.

Keywords

  • Star-like diblock copolymer | perovskite nanocrystals oxygen reduction reaction | density functional theory

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