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

A periodic, self-consistent planewave DFT study was carried out to explore the potential use of Pd 6 clusters supported on a boron nitride sheet as a catalyst for the selective decomposition of formic acid (HCOOH) to CO 2 and H 2. 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.
Authors:
 [1] ;  [1] ;  [1] ; ORCiD logo [2]
  1. Univ. degli Studi di Palermo (Italy)
  2. Univ. of Wisconsin, Madison, WI (United States)
Publication Date:
Grant/Contract Number:
FG02-05ER15731
Type:
Accepted Manuscript
Journal Name:
ChemCatChem
Additional Journal Information:
Journal Volume: 9; Journal Issue: 9; Journal ID: ISSN 1867-3880
Publisher:
ChemPubSoc Europe
Research Org:
Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Contributing Orgs:
National Energy Research Scientific Computing Center (NERSC); UW-Madison Center for High Throughput Computing (CHTC)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; boron nitride; DFT; formic acid; palladium; sub-nanometer clusters
OSTI Identifier:
1395997

Schimmenti, Roberto, Cortese, Remedios, Duca, Dario, and Mavrikakis, Manos. Boron Nitride-supported Sub-nanometer Pd 6 Clusters for Formic Acid Decomposition: A DFT Study. United States: N. p., Web. doi:10.1002/cctc.201700248.
Schimmenti, Roberto, Cortese, Remedios, Duca, Dario, & Mavrikakis, Manos. Boron Nitride-supported Sub-nanometer Pd 6 Clusters for Formic Acid Decomposition: A DFT Study. United States. doi:10.1002/cctc.201700248.
Schimmenti, Roberto, Cortese, Remedios, Duca, Dario, and Mavrikakis, Manos. 2017. "Boron Nitride-supported Sub-nanometer Pd 6 Clusters for Formic Acid Decomposition: A DFT Study". United States. doi:10.1002/cctc.201700248. https://www.osti.gov/servlets/purl/1395997.
@article{osti_1395997,
title = {Boron Nitride-supported Sub-nanometer Pd 6 Clusters for Formic Acid Decomposition: A DFT Study},
author = {Schimmenti, Roberto and Cortese, Remedios and Duca, Dario and Mavrikakis, Manos},
abstractNote = {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.},
doi = {10.1002/cctc.201700248},
journal = {ChemCatChem},
number = 9,
volume = 9,
place = {United States},
year = {2017},
month = {4}
}

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