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Title: Structure Sensitivity of Acetylene Semi-Hydrogenation on Pt Single Atoms and Subnanometer Clusters

Abstract

Oxide-supported Pt-group single atoms and clusters in the subnanometer size regime maximize the metal utilization and have shown extraordinary catalytic properties for many reactions including selective hydrogenation. Establishing relations between the metal nuclearity and electronic and catalytic properties is crucial for catalyst design. Here, we varied the nuclearity of Pt supported on TiO2 from single atoms to subnanometer clusters to larger nanoparticles to develop such relations for acetylene hydrogenation. We show that, in contrast to the low selectivity on large Pt nanoparticles, in the subnanometer size regime, Pt exhibits remarkably high selectivity to ethylene. Through a combination of X-ray photoelectron spectroscopy and calorimetry, we demonstrate that the origin of high selectivity is the decreased electron density on Pt and destabilization of C2H4 as the Pt nuclearity decreases. However, as the Pt nuclearity decreased, the activity for H2 activation and acetylene hydrogenation decreased, indicating a trade-off between activity and selectivity. Lastly, the results show that, while different properties emerge in the subnanometer regime, Pt supported on TiO2 appears to be bound by similar scaling and Brønsted–Evans–Polanyi relationships as on metal surfaces.

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]
  1. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1615019
Report Number(s):
PNNL-SA-144951
Journal ID: ISSN 2155-5435
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 9; Journal Issue: 12; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; single-atom catalysts; subnanometer clusters; H₂ activation; selective hydrogenation; X-ray photoelectron spectroscopy infrared spectroscopy; calorimetry; scanning transmission electron microscopy

Citation Formats

Kuo, Chun-Te, Lu, Yubing, Kovarik, Libor, Engelhard, Mark H., and Karim, Ayman M. Structure Sensitivity of Acetylene Semi-Hydrogenation on Pt Single Atoms and Subnanometer Clusters. United States: N. p., 2019. Web. doi:10.1021/acscatal.9b02840.
Kuo, Chun-Te, Lu, Yubing, Kovarik, Libor, Engelhard, Mark H., & Karim, Ayman M. Structure Sensitivity of Acetylene Semi-Hydrogenation on Pt Single Atoms and Subnanometer Clusters. United States. https://doi.org/10.1021/acscatal.9b02840
Kuo, Chun-Te, Lu, Yubing, Kovarik, Libor, Engelhard, Mark H., and Karim, Ayman M. Tue . "Structure Sensitivity of Acetylene Semi-Hydrogenation on Pt Single Atoms and Subnanometer Clusters". United States. https://doi.org/10.1021/acscatal.9b02840. https://www.osti.gov/servlets/purl/1615019.
@article{osti_1615019,
title = {Structure Sensitivity of Acetylene Semi-Hydrogenation on Pt Single Atoms and Subnanometer Clusters},
author = {Kuo, Chun-Te and Lu, Yubing and Kovarik, Libor and Engelhard, Mark H. and Karim, Ayman M.},
abstractNote = {Oxide-supported Pt-group single atoms and clusters in the subnanometer size regime maximize the metal utilization and have shown extraordinary catalytic properties for many reactions including selective hydrogenation. Establishing relations between the metal nuclearity and electronic and catalytic properties is crucial for catalyst design. Here, we varied the nuclearity of Pt supported on TiO2 from single atoms to subnanometer clusters to larger nanoparticles to develop such relations for acetylene hydrogenation. We show that, in contrast to the low selectivity on large Pt nanoparticles, in the subnanometer size regime, Pt exhibits remarkably high selectivity to ethylene. Through a combination of X-ray photoelectron spectroscopy and calorimetry, we demonstrate that the origin of high selectivity is the decreased electron density on Pt and destabilization of C2H4 as the Pt nuclearity decreases. However, as the Pt nuclearity decreased, the activity for H2 activation and acetylene hydrogenation decreased, indicating a trade-off between activity and selectivity. Lastly, the results show that, while different properties emerge in the subnanometer regime, Pt supported on TiO2 appears to be bound by similar scaling and Brønsted–Evans–Polanyi relationships as on metal surfaces.},
doi = {10.1021/acscatal.9b02840},
journal = {ACS Catalysis},
number = 12,
volume = 9,
place = {United States},
year = {2019},
month = {10}
}

Journal Article:
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Cited by: 96 works
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Figures / Tables:

Figure 1 Figure 1: HAADF-STEM images of Pt/TiO2 catalysts after H2 reduction at 350 °C. (a) 0.1% Pt/TiO2 (PtSA-0.7nm), (b) 1% Pt/TiO2 (Pt0.9nm), (c) 5% Pt/TiO2 (Pt1.5nm), (d) 10% Pt/TiO2 (Pt2.1nm).

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