Automated Detection and Characterization of Surface Restructuring Events in Bimetallic Catalysts

Lim, Jin Soo; Molinari, Nicola; Duanmu, Kaining; Sautet, Philippe; Kozinsky, Boris

doi:10.1021/acs.jpcc.9b04863

Automated Detection and Characterization of Surface Restructuring Events in Bimetallic Catalysts

Journal Article · Wed Jun 12 00:00:00 EDT 2019 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.9b04863· OSTI ID:1595403

^[1]; ^[2]; Duanmu, Kaining ^[3]; ^[3]; ^[4]

Harvard Univ., Cambridge, MA (United States); Harvard University
Harvard Univ., Cambridge, MA (United States)
Univ. of California, Los Angeles, CA (United States)
Harvard Univ., Cambridge, MA (United States); Robert Bosch LLC, Research and Technology Center, Cambridge, MA (United States)

Surface restructuring in bimetallic systems has recently been shown to play a crucial role in heterogeneous catalysis. In particular, the segregation in binary alloys can be reversed in the presence of strongly bound adsorbates. Mechanistic characterization of such restructuring phenomena at the atomic level remains scarce and challenging because of the large configurational space that must be explored. To this end, we propose an automated method to discover elementary surface restructuring processes in an unbiased fashion using Pd/Ag as an example. Here, we employ high-temperature classical molecular dynamics to rapidly detect restructuring events, isolate them, and optimize using density functional theory. In addition to confirming the known exchange descent mechanism, our systematic approach has revealed three new predominant classes of events at step edges of close-packed surfaces that have not been considered before: (1) vacancy insertion; (2) direct exchange; and (3) interlayer exchange. The discovered events enable us to construct the complete set of mechanistic pathways by which Pd is incorporated into the Ag host in vacuum at the single-atom limit. Finally, these atomistic insights provide a step toward systematic understanding and engineering of surface segregation dynamics in bimetallic catalysts.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC); Harvard Univ., Cambridge, MA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-05CH11231; AC05-00OR22725; SC0012573

OSTI ID:: 1595403

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 26 Vol. 123; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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