Formic Acid: A Hydrogen-Bonding Cocatalyst for Formate Decomposition

Chen, Benjamin W. J.; Mavrikakis, Manos

doi:10.1021/acscatal.0c02902

Title: Formic Acid: A Hydrogen-Bonding Cocatalyst for Formate Decomposition

Journal Article · Wed Aug 26 00:00:00 EDT 2020 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.0c02902· OSTI ID:1764608

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Univ. of Wisconsin, Madison, WI (United States)

Hydrogen bonding accelerates many catalytic reactions by orienting intermediates, stabilizing transition states, and even opening reaction pathways. However, most mechanistic studies regarding the decomposition of formic acid (FA), a promising hydrogen storage material, neglect hydrogen-bonding interactions even though FA is a strong hydrogen-bond donor and acceptor. Here, we probe the formation of bimolecular hydrogen-bonded complexes between FA and formate (FA–HCOO complexes) adsorbed on metal surfaces and how these complexes affect HCOO* decomposition. Using first-principles density functional theory (DFT) calculations on 12 close-packed (111)/(0001) and 8 open (100) surfaces of 12 transition metals—Ag, Au, Co, Cu, Ir, Ni, Os, Re, Pd, Pt, Rh, and Ru, we—show that FA–HCOO complexes are generally thermodynamically stable, even at elevated temperatures and pressures. We then illustrate that these complexes produce infrared spectroscopic signatures consistent with as yet unassigned experimental peaks. We last demonstrate that by stabilizing the dangling bond of monodentate HCOO*, these complexes significantly lower the barriers for rotation of HCOO* from a bidentate to a monodentate configuration, the rate-limiting step for HCOO* decomposition on many surfaces. FA thus acts as a cocatalyst for HCOO* decomposition. Our results may guide the community toward improved catalysts for reactions involving HCOO* such as FA decomposition, methanol steam reforming, and the water gas shift reaction. More broadly, our work highlights the ability of hydrogen bonding to modify the adsorbed structures of intermediates and lower the barriers for their reaction on heterogeneous catalysts. Lastly, this phenomenon can be relevant for other reactions involving ammonia, alcohols, and carboxylic acids.

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Research Organization:: Univ. of Wisconsin, Madison, WI (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: FG02-05ER15731; AC02-05CH11231

OSTI ID:: 1764608

Journal Information:: ACS Catalysis, Vol. 10, Issue 19; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Formic Acid: A Hydrogen-Bonding Cocatalyst for Formate Decomposition

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