Achieving Ultra-High Selectivity to Hydrogen Production from Formic Acid on Pd–Ag Alloys

Karatok, Mustafa; Ngan, Hio Tong; Jia, Xiwen; O’Connor, Christopher R.; Boscoboinik, J. Anibal; Stacchiola, Dario J.; Sautet, Philippe; Madix, Robert J.

doi:10.1021/jacs.2c11323

Achieving Ultra-High Selectivity to Hydrogen Production from Formic Acid on Pd–Ag Alloys

Journal Article · Sun Feb 26 23:00:00 EST 2023 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.2c11323· OSTI ID:1996246

^[1]; Ngan, Hio Tong ^[2]; ^[3]; ^[3]; ^[4]; ^[4]; ^[2]; ^[3]

Harvard University, Cambridge, MA (United States); Harvard University
University of California, Los Angeles, CA (United States)
Harvard University, Cambridge, MA (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States)

Palladium-silver based alloy catalysts have a great potential for CO-free hydrogen production from formic acid for fuel cell applications. However, the structural factors affecting the selectivity of formic acid decomposition is still debated. Herein, the decomposition pathways of formic acid on Pd-Ag alloys with different atomic configurations have been investigated to identify the alloy structures yielding high H₂ selectively. Several Pd_xAg_1-x surface alloys with various compositions were generated on a Pd(111) single crystal; their atomic distribution and electronic structure were determined by a combination of infrared reflection absorption spectroscopy (IRAS), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT). It was established that the Ag atoms with Pd neighbors are electronically altered, and the degree of alteration correlates with the number of nearest Pd. Temperature programmed reaction spectroscopy (TPRS) and DFT demonstrated that the electronically altered Ag domains create a new reaction pathway that selectively dehydrogenates formic acid. In contrast, Pd monomers surrounded by Ag are demonstrated to have a similar reactivity compared to pristine Pd(111), yielding CO and H₂O in addition to the dehydrogenation products. Furthermore, they bind to the produced CO weaker than pristine Pd, demonstrating an enhancement in resistance to CO poisoning. This work therefore shows that surface Ag domains modified by interaction with subsurface Pd are the key active sites for selective decomposition of formic acid, while surface Pd atoms are detrimental for selectivity. Hence the decomposition pathways can be tailored for CO-free H₂ production on Pd-Ag alloy systems.

View Accepted Manuscript (DOE)

Research Organization:: Harvard University, Cambridge, MA (United States)

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

Grant/Contract Number:: SC0012573

OSTI ID:: 1996246

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 9 Vol. 145; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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