Ethane dehydrogenation on pristine and AlOx decorated Pt stepped surfaces

Peng, Guowen; Gerceker, Duygu; Kumbhalkar, Mrunmayi; Dumesic, James A.; Mavrikakis, Manos

doi:10.1039/c8cy00398j

Title: Ethane dehydrogenation on pristine and AlO_x decorated Pt stepped surfaces

Journal Article · 29 March 2018 · Catalysis Science and Technology

DOI: https://doi.org/10.1039/c8cy00398j · OSTI ID:1543803

Peng, Guowen ^[1];

^[1]; Kumbhalkar, Mrunmayi ^[1];

^[1];

^[1]

Univ. of Wisconsin, Madison, WI (United States)

In this work, ethane dehydrogenation on pristine and AlO_x decorated Pt surfaces was studied using density functional theory (DFT) calculations and reaction kinetics experiments. Following the study of adsorption of fourteen distinct C₂H_x and CH_x species, the whole reaction network for ethane dehydrogenation on the terrace and the step of the pristine Pt(433) surface was systematically analyzed using DFT. We show that the under-coordinated step edge sites bind C₂H_x and CH_x species more strongly than terrace sites. These under-coordinated step sites facilitate deep dehydrogenation, resulting in accumulation of coke precursors on the surface and catalyst deactivation. We demonstrate that by decorating the step with AlO_x species the step edge sites can be blocked, leading to substantial suppression of deep dehydrogenation and coke formation. These findings were corroborated by reaction kinetics experiments where a four-fold enhancement of the turnover frequency for ethylene formation was measured on 10-cycle atomic layer deposited (ALD) alumina overcoated Pt/γ-Al₂O₃ catalyst compared to Pt/γ-Al₂O₃ without decoration with ALD-alumina. Our results suggest that AlO_x decorated Pt is a promising catalyst for alkane dehydrogenation and could have applications, including in endothermic cooling in hypersonic flights.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Center for Nanoscale Materials (CNM); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)

Sponsoring Organization:: US Air Force Office of Scientific Research (AFOSR); USDOD; USDOE Office of Science (SC); USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC02-05CH11231; AC02-06CH11357

OSTI ID:: 1543803

Journal Information:: Catalysis Science and Technology, Journal Name: Catalysis Science and Technology Journal Issue: 8 Vol. 8; ISSN 2044-4753

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Ethane dehydrogenation on pristine and AlO_x decorated Pt stepped surfaces