Reduction of Oxidized Pd/Ag(111) Surfaces by H2: Sensitivity to PdO Island Size and Dispersion

Karatok, Mustafa; Egle, Tobias; Mehar, Vikram; O’Connor, Christopher R.; Yu, Ming-Hung; Friend, Cynthia M.; Weaver, Jason F.

doi:10.1021/acscatal.0c03037

Reduction of Oxidized Pd/Ag(111) Surfaces by H₂: Sensitivity to PdO Island Size and Dispersion

Journal Article · Tue Aug 11 00:00:00 EDT 2020 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.0c03037· OSTI ID:1843582

^[1]; ^[2]; Mehar, Vikram ^[3]; O’Connor, Christopher R. ^[2]; Yu, Ming-Hung ^[3]; ^[2]; ^[3]

Harvard Univ., Cambridge, MA (United States); Harvard
Harvard Univ., Cambridge, MA (United States)
Univ. of Florida, Gainesville, FL (United States)

Understanding the migration of species across interfaces in bimetallic systems is key to exploiting their bifunctionality for chemical reactivity and heterogeneous catalysis. The present study demonstrates that the sizes and dispersion of oxidized Pd islands present on oxidized Ag(111) in addition to the concentration of active Pd sites have a significant influence on the rate of surface reduction by H₂. Two distinct types of Pd oxide islands were generated for this investigation and characterized using X-ray photoelectron spectroscopy and scanning tunneling microscopy. Small, uniformly-dispersed PdO_x islands (1-5 nm diameter) were created by depositing Pd onto AgO_x surfaces, while larger, non-uniformly dispersed PdO_x agglomerates (30-50 nm) were produced by depositing Pd on Ag(111) prior to oxidizing. Based on X-ray photoelectron spectroscopy, the small PdO_x islands have a higher concentration of undercoordinated Pd atoms than the large agglomerates. Both types of PdO_x are found to dramatically enhance the reduction of AgO_x by H₂ at 300 K due to the ability of the PdO_x to dissociate H₂; the pure AgO_x surfaces are unreactive toward H₂. The rate of reduction at 300 K is found to be 2-4 times larger for the AgO_x surface covered by small, uniformly dispersed PdO_x islands. The higher reactivity of this surface is attributed to enhanced migration of oxygen and hydrogen atoms between the PdO_x and AgO_x phases due to the sizes and high dispersion of the small PdO islands as well as the higher concentration of active Pd sites on the PdO_x. Furthermore, the results of this study demonstrate that reactant migration between co-existing surface phases is highly sensitive to both the intrinsic chemical activity and morphological properties of the active phase (PdO_x) and reveal that these properties can be significantly influenced by the method of synthesizing the oxidized bimetallic surfaces.

View Accepted Manuscript (DOE)

Research Organization:: Harvard Univ., Cambridge, MA (United States)

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

Grant/Contract Number:: SC0012573

OSTI ID:: 1843582

Alternate ID(s):: OSTI ID: 1802395

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 17 Vol. 10; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Reduction of Oxidized Pd/Ag(111) Surfaces by H2: Sensitivity to PdO Island Size and Dispersion

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Reduction of Oxidized Pd/Ag(111) Surfaces by H₂: Sensitivity to PdO Island Size and Dispersion