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Title: Pt 8 cluster on alumina under a pressure of hydrogen: Support-dependent reconstruction from first-principles global optimization

Abstract

Alumina supported Pt nano clusters under hydrogen environment play a crucial role for many heterogeneous catalysis applications. As such, we conducted grand canonical genetic algorithm (GCGA) simulations for supported Pt 8 clusters in hydrogen gas environment to study the intra-cluster, cluster-support, and cluster-adsorbate interactions. Two alumina surfaces, α-Al 2O 3(0001) and $γ$-Al 2O 3(100), and two conditions T=600°C, p H2 = 0.1bar and T=25°C, p H2 = 1.0 bar were considered corresponding to low and high hydrogen chemical potential $μ$ H, respectively. The low free energy ensemble of Pt 8 is decorated by a medium (2–12 H), resp. high (20–30 H), number of hydrogen atoms under equilibrium at low $μ$ H, respectively, high $μ$ H, and undergoes different morphology 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 $γ$-Al 2O 3(100), the exact opposite occurs, and Pt 8 clusters present one-layer 2D shapes at low $μ$ H and switch into compact 3D shapes under high $μ$ H, during which the Pt 8 cluster preserves moderate fluxionality. Further analysis reveals similar Pt–Pt bond length increase whenmore » switching from low $μ$ H to high $μ$ H on both surfaces, though morphology transformations are different. Electronic structure analysis shows the existence of bonding interactions between Pt and Lewis acidic Al 3+ 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) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division
OSTI Identifier:
1594248
Grant/Contract Number:  
SC0019152; DEAC02-05CH11231; 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: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:10.1063/1.5129296.
@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 nano clusters under hydrogen environment play a crucial role for many heterogeneous catalysis applications. As such, we conducted grand canonical genetic algorithm (GCGA) simulations for supported Pt8 clusters in hydrogen gas environment to study the intra-cluster, cluster-support, and cluster-adsorbate interactions. Two alumina surfaces, α-Al2O3(0001) and $γ$-Al2O3(100), and two conditions T=600°C, pH2 = 0.1bar and T=25°C, pH2 = 1.0 bar were considered corresponding to low and high hydrogen chemical potential $μ$H, respectively. The low free energy ensemble of Pt8 is decorated by a medium (2–12 H), resp. high (20–30 H), number of hydrogen atoms under equilibrium at low $μ$H, respectively, high $μ$H, and undergoes different morphology 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, and Pt8 clusters present one-layer 2D shapes at low $μ$H and switch into compact 3D shapes under high $μ$H, during which the Pt8 cluster preserves moderate fluxionality. Further analysis reveals similar Pt–Pt bond length increase when switching from low $μ$H to high $μ$H on both surfaces, though morphology 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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