Boron Nitride-supported Sub-nanometer Pd 6 Clusters for Formic Acid Decomposition: A DFT Study

Schimmenti, Roberto; Cortese, Remedios; Duca, Dario; Mavrikakis, Manos

doi:10.1002/cctc.201700248

Boron Nitride-supported Sub-nanometer Pd ₆ Clusters for Formic Acid Decomposition: A DFT Study

Journal Article · Tue Apr 25 00:00:00 EDT 2017 · ChemCatChem

DOI:https://doi.org/10.1002/cctc.201700248· OSTI ID:1395997

Schimmenti, Roberto ^[1]; Cortese, Remedios ^[2]; Duca, Dario ^[2]; ^[3]

Univ. degli Studi di Palermo (Italy); UW-Madison Department of Chemical and Biological Engineering
Univ. degli Studi di Palermo (Italy)
Univ. of Wisconsin, Madison, WI (United States)

A periodic, self-consistent planewave DFT study was carried out to explore the potential use of Pd₆ clusters supported on a boron nitride sheet as a catalyst for the selective decomposition of formic acid (HCOOH) to CO₂ and H₂. The competition between formate (HCOO) and carboxyl (COOH) paths on catalytic sites, with different proximities to the support, was studied. Based on energetics alone, the reaction may mainly follow the HCOO route. Slightly lower activation energies were found at the lateral sites of the cluster as compared to top face sites. This is particularly true for the bidentate to monodentate HCOO conversion. Through comparison of results with similar studies on HCOOH decomposition on extended Pd surfaces, it was demonstrated that the existence of undercoordinated sites in the sub-nanometer cluster could play a key role in preferentially stabilizing HCOO over COOH, which is a common CO precursor in this reaction. A hydrogen spillover mechanism was also investigated; migration toward the boron nitride support is not favorable, at least in the early stages of the reaction. However, hydrogen diffusion on the cluster has low barriers compared to those involved in formic acid decomposition.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Contributing Organization:: National Energy Research Scientific Computing Center (NERSC); UW-Madison Center for High Throughput Computing (CHTC)

Grant/Contract Number:: FG02-05ER15731

OSTI ID:: 1395997

Journal Information:: ChemCatChem, Journal Name: ChemCatChem Journal Issue: 9 Vol. 9; ISSN 1867-3880

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
DFT
boron nitride
formic acid
palladium
sub-nanometer clusters