Decoding reactive structures in dilute alloy catalysts

Marcella, Nicholas; Lim, Jin Soo; Płonka, Anna M.; Yan, George; Owen, Cameron J.; van der Hoeven, Jessi E. S.; Foucher, Alexandre C.; Ngan, Hio Tong; Torrisi, Steven B.; Marinkovic, Nebojsa S.; Stach, Eric A.; Weaver, Jason F.; Aizenberg, Joanna; Sautet, Philippe; Kozinsky, Boris; Frenkel, Anatoly I.

doi:10.1038/s41467-022-28366-w

Title: Decoding reactive structures in dilute alloy catalysts

Journal Article · 10 February 2022 · Nature Communications

DOI: https://doi.org/10.1038/s41467-022-28366-w · OSTI ID:1846156

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^[2]; Płonka, Anna M. ^[3]; Yan, George ^[4];

^[2]; van der Hoeven, Jessi E. S. ^[2];

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^[5]; Weaver, Jason F. ^[7];

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Stony Brook Univ., NY (United States); Harvard
Harvard Univ., Cambridge, MA (United States)
Stony Brook Univ., NY (United States)
Univ. of California, Los Angeles, CA (United States)
Univ. of Pennsylvania, Philadelphia, PA (United States)
Columbia Univ., New York, NY (United States)
Univ. of Florida, Gainesville, FL (United States)
Harvard Univ., Cambridge, MA (United States); Robert Bosch LLC, Research and Technology Center, Cambridge, MA (United States)
Stony Brook Univ., NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)

Rational catalyst design is crucial toward achieving more energy-efficient and sustainable catalytic processes. Understanding and modeling catalytic reaction pathways and kinetics require atomic level knowledge of the active sites. These structures often change dynamically during reactions and are difficult to decipher. A prototypical example is the hydrogen-deuterium exchange reaction catalyzed by dilute Pd-in-Au alloy nanoparticles. From a combination of catalytic activity measurements, machine learning-enabled spectroscopic analysis, and first-principles based kinetic modeling, we demonstrate that the active species are surface Pd ensembles containing only a few (from 1 to 3) Pd atoms. These species simultaneously explain the observed X-ray spectra and equate the experimental and theoretical values of the apparent activation energy. Remarkably, we find that the catalytic activity can be tuned on demand by controlling the size of the Pd ensembles through catalyst pretreatment. Our data-driven multimodal approach enables decoding of reactive structures in complex and dynamic alloy catalysts.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Harvard Univ., Cambridge, MA (United States); Northwestern Univ., Evanston, IL (United States)

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

Grant/Contract Number:: SC0012573; SC0012704; SC0021314

OSTI ID:: 1846156

Report Number(s):: BNL-222863-2022-JAAM

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 13; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Decoding reactive structures in dilute alloy catalysts

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