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Title: Surpassing the single-atom catalytic activity limit through paired Pt-O-Pt ensemble built from isolated Pt 1 atoms

Abstract

Despite the maximized metal dispersion offered by single-atom catalysts, further improvement of intrinsic activity can be hindered by the lack of neighboring metal atoms in these systems. Here we report the use of isolated Pt 1 atoms on ceria as “seeds” to develop a Pt-O-Pt ensemble, which is well-represented by a Pt 8O 14 model cluster that retains 100% metal dispersion. The Pt atom in the ensemble is 100–1000 times more active than their single-atom Pt 1/CeO 2 parent in catalyzing the low-temperature CO oxidation under oxygen-rich conditions. Rather than the Pt-O-Ce interfacial catalysis, the stable catalytic unit is the Pt-O-Pt site itself without participation of oxygen from the 10–30 nm-size ceria support. Similar Pt-O-Pt sites can be built on various ceria and even alumina, distinguishable by facile activation of oxygen through the paired Pt-O-Pt atoms. Extending this design to other reaction systems is a likely outcome of the findings reported here.

Authors:
 [1];  [2]; ORCiD logo [3]; ORCiD logo [4];  [5];  [1];  [1];  [1];  [6];  [6];  [5];  [7]; ORCiD logo [2]; ORCiD logo [6]
  1. Tianjin Univ., Tianjin (China)
  2. Univ. of Michigan, Ann Arbor, MI (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  4. Argonne National Lab. (ANL), Lemont, IL (United States)
  5. Tufts Univ., Medford, MA (United States)
  6. General Motors Global Research and Development, Warren, MI (United States)
  7. Tianjin Univ., Tianjin (China); Collaborative Innovation Center of Chemical Science and Engineering, Tianjin (China)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); National Natural Science Foundation of China (NNSFC); General Motors Research and Development
OSTI Identifier:
1558401
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Wang, Hui, Liu, Jin -Xun, Allard, Lawrence F., Lee, Sungsik, Liu, Jilei, Li, Hang, Wang, Jianqiang, Wang, Jun, Oh, Se H., Li, Wei, Flytzani-Stephanopoulos, Maria, Shen, Meiqing, Goldsmith, Bryan R., and Yang, Ming. Surpassing the single-atom catalytic activity limit through paired Pt-O-Pt ensemble built from isolated Pt1 atoms. United States: N. p., 2019. Web. doi:10.1038/s41467-019-11856-9.
Wang, Hui, Liu, Jin -Xun, Allard, Lawrence F., Lee, Sungsik, Liu, Jilei, Li, Hang, Wang, Jianqiang, Wang, Jun, Oh, Se H., Li, Wei, Flytzani-Stephanopoulos, Maria, Shen, Meiqing, Goldsmith, Bryan R., & Yang, Ming. Surpassing the single-atom catalytic activity limit through paired Pt-O-Pt ensemble built from isolated Pt1 atoms. United States. doi:10.1038/s41467-019-11856-9.
Wang, Hui, Liu, Jin -Xun, Allard, Lawrence F., Lee, Sungsik, Liu, Jilei, Li, Hang, Wang, Jianqiang, Wang, Jun, Oh, Se H., Li, Wei, Flytzani-Stephanopoulos, Maria, Shen, Meiqing, Goldsmith, Bryan R., and Yang, Ming. Fri . "Surpassing the single-atom catalytic activity limit through paired Pt-O-Pt ensemble built from isolated Pt1 atoms". United States. doi:10.1038/s41467-019-11856-9. https://www.osti.gov/servlets/purl/1558401.
@article{osti_1558401,
title = {Surpassing the single-atom catalytic activity limit through paired Pt-O-Pt ensemble built from isolated Pt1 atoms},
author = {Wang, Hui and Liu, Jin -Xun and Allard, Lawrence F. and Lee, Sungsik and Liu, Jilei and Li, Hang and Wang, Jianqiang and Wang, Jun and Oh, Se H. and Li, Wei and Flytzani-Stephanopoulos, Maria and Shen, Meiqing and Goldsmith, Bryan R. and Yang, Ming},
abstractNote = {Despite the maximized metal dispersion offered by single-atom catalysts, further improvement of intrinsic activity can be hindered by the lack of neighboring metal atoms in these systems. Here we report the use of isolated Pt1 atoms on ceria as “seeds” to develop a Pt-O-Pt ensemble, which is well-represented by a Pt8O14 model cluster that retains 100% metal dispersion. The Pt atom in the ensemble is 100–1000 times more active than their single-atom Pt1/CeO2 parent in catalyzing the low-temperature CO oxidation under oxygen-rich conditions. Rather than the Pt-O-Ce interfacial catalysis, the stable catalytic unit is the Pt-O-Pt site itself without participation of oxygen from the 10–30 nm-size ceria support. Similar Pt-O-Pt sites can be built on various ceria and even alumina, distinguishable by facile activation of oxygen through the paired Pt-O-Pt atoms. Extending this design to other reaction systems is a likely outcome of the findings reported here.},
doi = {10.1038/s41467-019-11856-9},
journal = {Nature Communications},
issn = {2041-1723},
number = 1,
volume = 10,
place = {United States},
year = {2019},
month = {8}
}

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Figures / Tables:

Fig. 11 Fig. 11: Direct measurements of the Pt1/CeO2 and Pt-O-Pt/CeO2 catalysts. a, b Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) images for the Pt1/CeO2-a and Pt-O-Pt/CeO2-a catalysts (shown images were recorded at ×10M and ×6M original magnifications, respectively). Yellow circles and squares are used to highlight the single-atom Pt1more » and the Pt-O-Pt ensemble, respectively. c CO oxidation light-off performance ([CO]= 1000 ppm, [O2]= 5%, balanced with N2 at a contact time of 2,400,000mL/gcat//h). d Arrhenius-type plot of CO oxidation rates at different temperatures with apparent activation energies (Eapp) shown« less

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