Oxophilicity Drives Oxygen Transfer at a Palladium–Silver Interface for Increased CO Oxidation Activity

Mehar, Vikram; Almithn, Abdulrahman; Egle, Tobias; Yu, Ming-Hung; O’Connor, Christopher R.; Karatok, Mustafa; Madix, Robert J.; Hibbitts, David; Weaver, Jason F.

doi:10.1021/acscatal.0c03885

Oxophilicity Drives Oxygen Transfer at a Palladium–Silver Interface for Increased CO Oxidation Activity

Journal Article · Sun Nov 15 23:00:00 EST 2020 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.0c03885· OSTI ID:1845312

Mehar, Vikram ^[1]; Almithn, Abdulrahman ^[2]; ^[3]; Yu, Ming-Hung ^[4]; O’Connor, Christopher R. ^[3]; Karatok, Mustafa ^[3]; ^[3]; ^[4]; ^[4]

Univ. of Florida, Gainesville, FL (United States); Harvard
Univ. of Florida, Gainesville, FL (United States); King Faisal University, Hofuf (Saudi Arabia)
Harvard Univ., Cambridge, MA (United States)
Univ. of Florida, Gainesville, FL (United States)

A single-layer AgO_x phase grown on Ag(111) efficiently transfers oxygen to Pd domains at room temperature, rendering the Pd-decorated surface highly reactive toward CO oxidation. Here, oxygen transfer from AgO_x to Pd and the surface reactivity toward CO were investigated as a function of the Pd coverage using X-ray photoelectron spectroscopy, surface infrared spectroscopy of adsorbed CO, temperature-programmed reaction spectroscopy, and density functional theory (DFT) calculations. Our results show that all of the oxygen from the AgO_x layer (~0.375 monolayer) migrates to the surface of Pd during formation of a nearly complete Pd bilayer at 300 K and that the oxygen coverages generated on Pd increase as the Pd cluster size decreases, reaching values that exceed the oxygen concentration in the AgO_x layer by as much as a factor of 2. Experimental measurements and DFT calculations show that preferential binding of oxygen on the edges of the Pd clusters enhances the oxygen coverage on Pd clusters of decreasing size and produces a heterogeneous spatial distribution of oxygen. CO adsorbs in high coverages at 100 K by binding on both the terraces and O-rich edges of the Pd clusters. During subsequent heating, oxidation of the adsorbed CO consumes nearly all of the oxygen that transferred from AgO_x to the Pd domains; in contrast, the pure AgO_x layer exhibits limited reactivity toward CO adsorbed at 100 K. These results demonstrate that differences in oxophilicity drive facile oxygen transfer from Ag to the edges of Pd nanoclusters and thereby give rise to an efficient pathway for CO oxidation on bimetallic PdAg surfaces. The cooperation between the Pd and Ag domains results in near-interfacial chemistry that may be broadly important in catalysis by bimetallic alloys.

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:: 1845312

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 23 Vol. 10; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Oxophilicity Drives Oxygen Transfer at a Palladium–Silver Interface for Increased CO Oxidation Activity

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