Interpreting the Operando X-ray Absorption Near-Edge Structure of Supported Cu and CuPd Clusters in Conditions of Oxidative Dehydrogenation of Propane: Dynamic Changes in Composition and Size

Poths, Patricia; Sun, Geng; Sautet, Philippe; Alexandrova, Anastassia N.

doi:10.1021/acs.jpcc.1c10356

Interpreting the Operando X-ray Absorption Near-Edge Structure of Supported Cu and CuPd Clusters in Conditions of Oxidative Dehydrogenation of Propane: Dynamic Changes in Composition and Size

Journal Article · Wed Jan 19 23:00:00 EST 2022 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.1c10356· OSTI ID:1968776

^[1]; Sun, Geng ^[2]; ^[3]; ^[3]

Univ. of California, Los Angeles, CA (United States); UCLA
Univ. of California, Los Angeles, CA (United States)
Univ. of California, Los Angeles, CA (United States); California NanoSystems Inst., Los Angeles, CA (United States)

Supported subnano-cluster catalysts are highly dynamic, developing true active sites only under the pressures and temperatures of reaction conditions. Operando X-ray absorption near-edge structure (XANES) spectroscopy can track changes in the oxidation state and the local environment of cluster atoms, providing insight into the development of these active sites. While bulk metal, oxide, and hydroxide standards are often used for fitting experimental XANES spectra to obtain average oxidation states, we recently showed that computed cluster standards of relevant compositions are a more suitable basis, producing more accurate fits. Here, we theoretically interpret the operando XANES of supported Cu₃Pd and Cu₄ clusters during temperature-programmed reaction (TPRx) of oxidative dehydrogenation of propane. We use an expanded basis set including both globally optimized computed clusters and bulk standards. Not only can we track reversible composition/oxidation state change with temperature, but also the irreversible growth of the bulk fraction upon heating, which we attribute to cluster sintering. This has important implications for the mechanism of the catalyzed reaction and the nature of the available active sites. Here, we propose that operando XANES provides most significant insight into the nature of supported cluster catalysts in reaction conditions when interpreted using mixed computed cluster and bulk standards.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of California, Los Angeles, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0019152

OSTI ID:: 1968776

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 4 Vol. 126; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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