Revealing the structure of a catalytic combustion active-site ensemble combining uniform nanocrystal catalysts and theory insights

Yang, An-Chih; Choksi, Tej; Streibel, Verena; Aljama, Hassan; Wrasman, Cody J.; Roling, Luke T.; Roling, Luke T.; Thomas, Dionne; Bare, Simon R.; Sánchez-Carrera, Roel S.; Schäfer, Ansgar; Li, Yuejin; Abild-Pedersen, Frank; Cargnello, Matteo

doi:10.1073/pnas.2002342117

Revealing the structure of a catalytic combustion active-site ensemble combining uniform nanocrystal catalysts and theory insights

Journal Article · Wed Jun 17 00:00:00 EDT 2020 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.2002342117· OSTI ID:1647095

Yang, An-Chih ^[1]; ^[1]; ^[1]; Aljama, Hassan ^[1]; Wrasman, Cody J. ^[2]; ^[3]; ^[2]; Thomas, Dionne ^[4]; ^[5]; Sánchez-Carrera, Roel S. ^[6]; Schäfer, Ansgar ^[7]; Li, Yuejin ^[8]; Abild-Pedersen, Frank ^[5]; ^[2]

Stanford Univ., CA (United States). Dept. of Chemical Engineering and SUNCAT Center for Interface Science and Catalysis; SLAC National Accelerator Lab., Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis
Stanford Univ., CA (United States). Dept. of Chemical Engineering and SUNCAT Center for Interface Science and Catalysis
Stanford Univ., CA (United States). Dept. of Chemical Engineering and SUNCAT Center for Interface Science and Catalysis; SLAC National Accelerator Lab., Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis; Iowa State Univ., Ames, IA (United States). Dept. of Chemical and Biological Engineering
Stanford Univ., CA (United States). Dept. of Chemical Engineering
SLAC National Accelerator Lab., Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis
BASF Corporation, Tarrytown, NY (United States). Digitalization of Research & Development
BASF Corporation, Ludwigshafen (Germany). Digitalization of Research & Development
BASF Corporation, Iselin, NJ (United States). Environmental Catalysis R&D

Supported metal catalysts are extensively used in industrial and environmental applications. To improve their performance, it is crucial to identify the most active sites. This identification is, however, made challenging by the presence of a large number of potential surface structures that complicate such an assignment. Often, the active site is formed by an ensemble of atoms, thus introducing further complications in its identification. Being able to produce uniform structures and identify the ones that are responsible for the catalyst performance is a crucial goal. Here, we utilize a combination of uniform Pd/Pt nanocrystal catalysts and theory to reveal the catalytic active-site ensemble in highly active propene combustion materials. Using colloidal chemistry to exquisitely control nanoparticle size, we find that intrinsic rates for propene combustion in the presence of water increase monotonically with particle size on Pt-rich catalysts, suggesting that the reaction is structure dependent. We also reveal that water has a near-zero or mildly positive reaction rate order over Pd/Pt catalysts. Theory insights allow us to determine that the interaction of water with extended terraces present in large particles leads to the formation of step sites on metallic surfaces. These specific step-edge sites are responsible for the efficient combustion of propene at low temperature. This work reveals an elusive geometric ensemble, thus clearly identifying the active site in alkene combustion catalysts. These insights demonstrate how the combination of uniform catalysts and theory can provide a much deeper understanding of active-site geometry for many applications

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: Alexander von Humboldt Foundation; California Research Alliance; National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1647095

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Issue: 26 Vol. 117; ISSN 0027-8424

Publisher:: National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
active site
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combustion
nanocrystal
theory

Revealing the structure of a catalytic combustion active-site ensemble combining uniform nanocrystal catalysts and theory insights

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References (48)

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