Tuning reactivity layer-by-layer: formic acid activation on Ag/Pd(111)

Karatok, Mustafa; Duanmu, Kaining; O'Connor, Christopher R.; Boscoboinik, Jorge Anibal; Sautet, Philippe; Madix, Robert J.; Friend, Cynthia M.

doi:10.1039/d0sc01461c

Title: Tuning reactivity layer-by-layer: formic acid activation on Ag/Pd(111)

Journal Article · 20 April 2020 · Chemical Science

DOI: https://doi.org/10.1039/d0sc01461c · OSTI ID:1616354

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Harvard Univ., Cambridge, MA (United States)
Univ. of California, Los Angeles, CA (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)

The potential for tuning the electronic structure of materials to control reactivity and selectivity in heterogenous catalysis has driven interest in ultrathin metal films which may differ from their bulk form. Herein, a 1-atomic layer Ag film on Pd(111) (Ag/Pd(111)) is demonstrated to have dramatically different reactivity towards formic acid compared to bulk Ag. Formic acid decomposition is of interest as a source of H₂ for fuel cell applications and modification of Pd by Ag reduces poisoning by CO and increases the selectivity for H₂ formation. Formic acid reacts below room temperature on the 1-atomic layer Ag film, whereas no reaction occurs on pristine bulk Ag. Notably, 2 monolayer films of Ag again become unreactive towards formic acid, indicating a reversion to bulk behavior. A combination of infrared reflection absorption spectroscopy (IRRAS), X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) was used to establish that the Ag monolayer is continuous and electronically modified compared to bulk Ag. The work establishes a demonstration of the altered electronic structure of Ag monolayers on Pd(111) and an associated change in reactivity. The effect on reactivity only persists for the first layer, demonstrating the need for precise control of materials to exploit the modification in electronic properties.

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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:: 1616354

Alternate ID(s):: OSTI ID: 1677678; OSTI ID: 1843585

Journal Information:: Chemical Science, Vol. 11, Issue 25; ISSN 2041-6520

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 6 works

Citation information provided by
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