HCOOH Decomposition on Sub-Nanometer Pd6 Cluster Catalysts: The Effect of Defective Boron Nitride Supports Through First Principles

Schimmenti, Roberto; Mavrikakis, Manos

doi:10.1016/j.apcatb.2020.119392

HCOOH Decomposition on Sub-Nanometer Pd₆ Cluster Catalysts: The Effect of Defective Boron Nitride Supports Through First Principles

Journal Article · Sat Aug 15 00:00:00 EDT 2020 · Applied Catalysis B: Environmental

DOI:https://doi.org/10.1016/j.apcatb.2020.119392· OSTI ID:1764616

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Univ. of Wisconsin, Madison, WI (United States); University of Wisconsin-Madison Department of Chemical and Biological Engineering
Univ. of Wisconsin, Madison, WI (United States)

The catalytic properties of a hexagonal boron nitride- (h-BN) supported Pd₆ sub-nanometer cluster in the context of formic acid (HCOOH) decomposition were studied by means of periodic Density Functional Theory (DFT) calculations. The effect of support defectivity – boron (h-B_vN) and nitrogen (h-BN_v) monovacancies – on the competition between the formate (HCOO)- and carboxyl (COOH)-mediated decomposition pathways was analyzed. Defects are responsible for charge-transfer leading to a positively or negatively charged cluster, and open new reactive channels in which vacancy-mediated dehydrogenation pathways can occur. Pd₆ cluster reconstructions, induced by the adsorption of reaction intermediates and by the presence of monovacancies in the support, greatly stabilize the formation of CO from COOH, which could drastically decrease the selectivity towards hydrogen production. Here, a simplified descriptor-based analysis, based on selected thermochemical quantities calculated on charged cluster models, suggests that Pd₆ sub-nanometer clusters supported on pristine h-BN and h-BN_v can be more selective than Pd₆ supported on defective h-B_vN towards HCOOH dehydrogenation.

View Accepted Manuscript (DOE)

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

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

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

OSTI ID:: 1764616

Alternate ID(s):: OSTI ID: 1778305

Journal Information:: Applied Catalysis B: Environmental, Journal Name: Applied Catalysis B: Environmental Vol. 280; ISSN 0926-3373

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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HCOOH Decomposition on Sub-Nanometer Pd6 Cluster Catalysts: The Effect of Defective Boron Nitride Supports Through First Principles

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References (53)

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