Cluster Expansion Method for Simulating Realistic Size of Nanoparticle Catalysts with an Application in CO2 Electroreduction

Taedaehyeong Eom, Won June Kim, Hyung Kyu Lim, Myung Hoon Han, Kyeong Hwan Han, Eok Kyun Lee, Sébastien Lebègue, Yun Jeong Hwang, Byoung Koun Min, Hyungjun Kim

Research output: Contribution to journalArticlepeer-review

16 Citations (Scopus)


For the last several decades, there has been a rapid development of nanoscience and nanotechnology. In particular, nanoparticles (NPs) are applied in various catalyst problems, where their enormously large surface-to-volume ratio not only is advantageous for high catalytic performance but also allows the quantum size effect to play a key role in modifying their chemical properties. However, when understanding the size effect of NPs on the catalytic properties by employing density functional theory (DFT) calculations, there has been an obvious experiment-theory gap in simulating nanocatalysts with realistic sizes. In this study, we developed a new simulation method based on the cluster expansion model, namely, CE-np, which enables efficient and accurate calculations of the intermediate binding energies for various sizes of NPs. We then applied CE-np to investigate the electrochemical CO2 reduction reaction (CO2RR) of gold NPs (AuNPs). CE-np reproduces not only DFT-level accuracies in predicting the intermediate binding energies on the NPs and slab surfaces but also the experimental behavior of catalytic activity and selectivity of AuNP catalysts. Because of the high computational efficiency of CE-np (without sacrificing the accuracy level of DFT), we performed the most exhaustive search on all possible on-top binding sites of AuNPs to unveil the complicated relations between the catalytic performance (activity and selectivity) and the NP properties (shape and size). This also highlights for the first time the catalytic importance of the near-edge sites, that is, active sites on the facets that are very close to the edges. We anticipate that our methodological development and several new findings on the CO2RR activity of AuNPs will provide advances in developing CO2 electrochemical reduction technologies based on NPs.

Original languageEnglish
Pages (from-to)9245-9254
Number of pages10
JournalJournal of Physical Chemistry C
Issue number16
Publication statusPublished - 2018 Apr 26

Bibliographical note

Funding Information:
This work was supported by the Creative Materials Discovery Program (grant 2017M3D1A1039378), Nanomaterial Technology Development Program (grant 2016M3A7B4025414), and Technology Development Program to Solve Climate Changes (grant 2015M1A2A2056561) through the National Research Foundation of Korea (NRF).

Publisher Copyright:
© 2018 American Chemical Society.

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • General Energy
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films


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