Initial Reduction of the PdO(101) Surface: Role of Oxygen Vacancy Formation Kinetics

Kim, Minkyu; Pan, Li; Weaver, Jason F.; Asthagiri, Aravind

doi:10.1021/acs.jpcc.8b08226

Initial Reduction of the PdO(101) Surface: Role of Oxygen Vacancy Formation Kinetics

Journal Article · Fri Oct 19 04:00:00 EDT 2018 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.8b08226· OSTI ID:1593972

Kim, Minkyu ^[1]; Pan, Li ^[2]; ^[3]; ^[2]

The Ohio State Univ., Columbus, OH (United States); University of Florida
The Ohio State Univ., Columbus, OH (United States)
Univ. of Florida, Gainesville, FL (United States)

Here, we investigated the initial thermal reduction of the PdO(101) surface using density functional theory (DFT) calculations. The defect-free PdO(101) surface consists of parallel rows of undercoordinated Pd and O atoms (Pd_cus and O_cus, respectively). DFT was used to map out the elementary processes of O_cus vacancy formation, oxygen surface atom diffusion along the Pd_cus rows, and various O₂ formation pathways. Because oxygen vacancies form during the reduction of the surface, the elementary processes were examined with and without the presence of adjacent O_cus vacancies. DFT calculations show that the presence of oxygen vacancies strongly affects the barriers of adjacent surface processes. Barriers for O vacancy formation are reduced by nearly 50% with an adjacent O vacancy. The barrier for O₂ formation along the Pd_cus row drops from 1.54 eV on the defect-free PdO(101) surface to 0.81 eV in the presence of an O_cus vacancy dimer. Yet, the presence of O_cus vacancies also leads to more strongly bound O₂ on the Pd_cus row. The strong neighbor effect of O vacancies on the PdO(101) surface will favor the growth of O vacancy chains and increase the rate of thermal reduction of the surface, both features that have been observed in recent ultrahigh vacuum isothermal reduction experiments of the PdO(101) surface.

Research Organization:: Univ. of Florida, Gainesville, FL (United States)

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

DOE Contract Number:: FG02-03ER15478

OSTI ID:: 1593972

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 45 Vol. 122; ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

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