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Title: Pt8 cluster on alumina under a pressure of hydrogen: Support-dependent reconstruction from first-principles global optimization

Abstract

Alumina supported Pt nanoclusters under a hydrogen environment play a crucial role in many heterogeneous catalysis applications. We conducted grand canonical genetic algorithm simulations for supported Pt8 clusters in a hydrogen gas environment to study the intracluster, cluster-support, and cluster-adsorbate interactions. Two alumina surfaces, α-Al2O3(0001) and γ-Al2O3(100), and two conditions, T = 600 °C, pH2 = 0.1 bar and T = 25 °C, pH2 = 1.0 bar, were considered corresponding to low and high hydrogen chemical potential μH, respectively. The low free energy ensemble of Pt8 is decorated by a medium (2-12 H), respectively, high (20-30 H), number of hydrogen atoms under equilibrium at low μH, respectively, high μH, and undergoes different morphological transformations on the two surfaces. On α-Al2O3(0001), Pt8 is mostly 3D but very fluxional in structure at low μH and converts to open one-layer 2D structures with minimal fluxionality at high μH, whereas on γ-Al2O3(100), the exact opposite occurs: Pt8 clusters present one-layer 2D shapes at low μH and switch to compact 3D shapes under high μH, during which the Pt8 cluster preserves moderate fluxionality. Further analysis reveals a similar Pt-Pt bond length increase when switching from low μH to high μH on both surfaces although morphologicalmore » transformations are different. Electronic structure analysis shows the existence of bonding interactions between Pt and Lewis acidic Al3+ sites along with the Pt-O interaction, which implies the necessity to include Al neighbors to discuss the electronic structure of small Pt clusters.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]
  1. Univ. of California, Los Angeles, CA (United States)
  2. Univ. of California, Los Angeles, CA (United States); California NanoSystems Inst., Los Angeles, CA (United States)
Publication Date:
Research Org.:
Univ. of California, Los Angeles, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
OSTI Identifier:
1594248
Alternate Identifier(s):
OSTI ID: 1607566; OSTI ID: 1755392
Grant/Contract Number:  
SC0019152; AC02-05CH11231; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 19; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Global optimization; Pt cluster; alumina; cluster fluxionality

Citation Formats

Sun, Geng, Alexandrova, Anastassia N., and Sautet, Philippe. Pt8 cluster on alumina under a pressure of hydrogen: Support-dependent reconstruction from first-principles global optimization. United States: N. p., 2019. Web. doi:10.1063/1.5129296.
Sun, Geng, Alexandrova, Anastassia N., & Sautet, Philippe. Pt8 cluster on alumina under a pressure of hydrogen: Support-dependent reconstruction from first-principles global optimization. United States. doi:https://doi.org/10.1063/1.5129296
Sun, Geng, Alexandrova, Anastassia N., and Sautet, Philippe. Wed . "Pt8 cluster on alumina under a pressure of hydrogen: Support-dependent reconstruction from first-principles global optimization". United States. doi:https://doi.org/10.1063/1.5129296. https://www.osti.gov/servlets/purl/1594248.
@article{osti_1594248,
title = {Pt8 cluster on alumina under a pressure of hydrogen: Support-dependent reconstruction from first-principles global optimization},
author = {Sun, Geng and Alexandrova, Anastassia N. and Sautet, Philippe},
abstractNote = {Alumina supported Pt nanoclusters under a hydrogen environment play a crucial role in many heterogeneous catalysis applications. We conducted grand canonical genetic algorithm simulations for supported Pt8 clusters in a hydrogen gas environment to study the intracluster, cluster-support, and cluster-adsorbate interactions. Two alumina surfaces, α-Al2O3(0001) and γ-Al2O3(100), and two conditions, T = 600 °C, pH2 = 0.1 bar and T = 25 °C, pH2 = 1.0 bar, were considered corresponding to low and high hydrogen chemical potential μH, respectively. The low free energy ensemble of Pt8 is decorated by a medium (2-12 H), respectively, high (20-30 H), number of hydrogen atoms under equilibrium at low μH, respectively, high μH, and undergoes different morphological transformations on the two surfaces. On α-Al2O3(0001), Pt8 is mostly 3D but very fluxional in structure at low μH and converts to open one-layer 2D structures with minimal fluxionality at high μH, whereas on γ-Al2O3(100), the exact opposite occurs: Pt8 clusters present one-layer 2D shapes at low μH and switch to compact 3D shapes under high μH, during which the Pt8 cluster preserves moderate fluxionality. Further analysis reveals a similar Pt-Pt bond length increase when switching from low μH to high μH on both surfaces although morphological transformations are different. Electronic structure analysis shows the existence of bonding interactions between Pt and Lewis acidic Al3+ sites along with the Pt-O interaction, which implies the necessity to include Al neighbors to discuss the electronic structure of small Pt clusters.},
doi = {10.1063/1.5129296},
journal = {Journal of Chemical Physics},
number = 19,
volume = 151,
place = {United States},
year = {2019},
month = {11}
}

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