A Theory-Guided X-ray Absorption Spectroscopy Approach for Identifying Active Sites in Atomically Dispersed Transition-Metal Catalysts

Chen, Yizhen; Rana, Rachita; Sours, Tyler; Vila, Fernando D.; Cao, Shaohong; Blum, Thomas; Hong, Jiyun; Hoffman, Adam S.; Fang, Chia-Yu; Huang, Zhennan; Shang, Chunyan; Wang, Chuanhao; Zeng, Jie; Chi, Miaofang; Kronawitter, Coleman X.; Bare, Simon R.; Gates, Bruce C.; Kulkarni, Ambarish R.

doi:10.1021/jacs.1c07116

Title: A Theory-Guided X-ray Absorption Spectroscopy Approach for Identifying Active Sites in Atomically Dispersed Transition-Metal Catalysts

Journal Article · Mon Nov 22 00:00:00 EST 2021 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.1c07116· OSTI ID:1863240

Chen, Yizhen ^[1]; Rana, Rachita ^[1]; Sours, Tyler ^[1];

^[2];

^[3]; Blum, Thomas ^[4]; Hong, Jiyun ^[5]; Hoffman, Adam S. ^[5]; Fang, Chia-Yu ^[1]; Huang, Zhennan ^[3]; Shang, Chunyan ^[6];

^[6];

^[3];

^[1];

^[5];

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^[1]

Univ. of California, Davis, CA (United States)
Univ. of Washington, Seattle, WA (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of California, Irvine, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Univ. of Science and Technology of China, Hefei (China)

Atomically dispersed supported metal catalysts offer new properties and the benefits of maximized metal accessibility and utilization. The characterization of these materials, however, remains challenging. Using atomically dispersed platinum supported on crystalline MgO (chosen for its well-defined bonding sites) as a prototypical example, we demonstrate in this work how systematic density functional theory calculations for assessing all the potentially stable platinum sites, combined with automated analysis of extended X-ray absorption fine structure (EXAFS) spectra, leads to unbiased identification of isolated, surface-enveloped platinum cations as the catalytic species for CO oxidation. The catalyst has been characterized by atomic-resolution imaging and EXAFS and high-energy resolution fluorescence detection X-ray absorption near edge spectroscopy. The proposed platinum sites are in agreement with experiment. This theory-guided workflow leads to rigorously determined structural models and provides a more detailed picture of the structure of the catalytically active site than what is currently possible with conventional EXAFS analyses. As this approach is efficient and agnostic to the metal, support, and catalytic reaction, we posit that it will be of broad interest to the materials characterization and catalysis communities.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; China Scholarship Council (CSC); National Science Foundation (NSF)

Grant/Contract Number:: AC02-76SF00515; FG02-04ER15513; AC05-00OR22725; SC0020320; AC02-05CH11231; ACI-1548562

OSTI ID:: 1863240

Alternate ID(s):: OSTI ID: 1846513

Journal Information:: Journal of the American Chemical Society, Vol. 143, Issue 48; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Magnesium oxide
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Title: A Theory-Guided X-ray Absorption Spectroscopy Approach for Identifying Active Sites in Atomically Dispersed Transition-Metal Catalysts

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