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Title: Nucleation of Cu n ( n = 1–5) Clusters and Equilibrium Morphology of Cu Particles Supported on CeO 2 Surface: A Density Functional Theory Study

Abstract

In the present work, the interactions between Cun (n=1~4) clusters and three low-index structural CeO2 (111, 110, 100) surfaces were investigated using density functional theory calculations. The atomic Cu prefers to aggregate into large clusters on the CeO2(111) surface while it is unfavorable on both CeO2(110) and CeO2(100) surfaces. Once the planar Cu4-p cluster is formed, it would convert into the 3D tetrahedral Cu4-t cluster on CeO2(110) and CeO2(111) surfaces, i.e., 2D to 3D transition growth is thermodynamically favorable and kinetically feasible on CeO2(110) and CeO2(111) surfaces. The effects of ceria support structure on the morphology of the large Cu nanoparticle was examined using calculated adhesion and interfacial energies of periodic Cu(khl)/CeO2 model systems. The calculated macroscopic contact angles (? > 100?) of various model systems suggest that the supported Cu nanoparticle is in bad wetting condition. Finally, the morphologies of large Cu nanoparticles on different CeO2 surfaces were predicted using Wulff-Kaichew construction principle.

Authors:
 [1];  [2];  [3];  [4]; ORCiD logo [5]
  1. Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99352, United States; State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China; Huaneng Clean Energy Research Institute, Beijing 102209, China
  2. Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99352, United States; State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China; College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100022, China
  3. State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China; College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100022, China
  4. State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China
  5. Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99352, United States
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1496624
Report Number(s):
PNNL-SA-137468
Journal ID: ISSN 1932-7447
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 48; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
Cu/CeO2 catalyst, Adsorption and nucleation, DFT calculation, Wulff-Kaichew construction

Citation Formats

Ren, Zhibo, Liu, Ning, Chen, Biaohua, Li, Jianwei, and Mei, Donghai. Nucleation of Cu n ( n = 1–5) Clusters and Equilibrium Morphology of Cu Particles Supported on CeO 2 Surface: A Density Functional Theory Study. United States: N. p., 2018. Web. doi:10.1021/acs.jpcc.8b07993.
Ren, Zhibo, Liu, Ning, Chen, Biaohua, Li, Jianwei, & Mei, Donghai. Nucleation of Cu n ( n = 1–5) Clusters and Equilibrium Morphology of Cu Particles Supported on CeO 2 Surface: A Density Functional Theory Study. United States. doi:10.1021/acs.jpcc.8b07993.
Ren, Zhibo, Liu, Ning, Chen, Biaohua, Li, Jianwei, and Mei, Donghai. Tue . "Nucleation of Cu n ( n = 1–5) Clusters and Equilibrium Morphology of Cu Particles Supported on CeO 2 Surface: A Density Functional Theory Study". United States. doi:10.1021/acs.jpcc.8b07993.
@article{osti_1496624,
title = {Nucleation of Cu n ( n = 1–5) Clusters and Equilibrium Morphology of Cu Particles Supported on CeO 2 Surface: A Density Functional Theory Study},
author = {Ren, Zhibo and Liu, Ning and Chen, Biaohua and Li, Jianwei and Mei, Donghai},
abstractNote = {In the present work, the interactions between Cun (n=1~4) clusters and three low-index structural CeO2 (111, 110, 100) surfaces were investigated using density functional theory calculations. The atomic Cu prefers to aggregate into large clusters on the CeO2(111) surface while it is unfavorable on both CeO2(110) and CeO2(100) surfaces. Once the planar Cu4-p cluster is formed, it would convert into the 3D tetrahedral Cu4-t cluster on CeO2(110) and CeO2(111) surfaces, i.e., 2D to 3D transition growth is thermodynamically favorable and kinetically feasible on CeO2(110) and CeO2(111) surfaces. The effects of ceria support structure on the morphology of the large Cu nanoparticle was examined using calculated adhesion and interfacial energies of periodic Cu(khl)/CeO2 model systems. The calculated macroscopic contact angles (? > 100?) of various model systems suggest that the supported Cu nanoparticle is in bad wetting condition. Finally, the morphologies of large Cu nanoparticles on different CeO2 surfaces were predicted using Wulff-Kaichew construction principle.},
doi = {10.1021/acs.jpcc.8b07993},
journal = {Journal of Physical Chemistry. C},
issn = {1932-7447},
number = 48,
volume = 122,
place = {United States},
year = {2018},
month = {11}
}