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

Title: 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 ^[1]; Duca, Dario ^[1];

^[2]

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.

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

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

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, Vol. 9, Issue 9; ISSN 1867-3880

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 22 works

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References (44)

Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Palladium-atom catalyzed formic acid decomposition and the switch of reaction mechanism with temperature He, Nan; Li, Zhen Hua Physical Chemistry Chemical Physics, Vol. 18, Issue 15 https://doi.org/10.1039/C6CP00186F	journal	January 2016
Particle size effects in selective oxidation of lactose with Pd/h-BN catalysts Meyer, Nathalie; Pirson, Damien; Devillers, Michel Applied Catalysis A: General, Vol. 467 https://doi.org/10.1016/j.apcata.2013.07.045	journal	October 2013
A Comprehensive Study of Formic Acid Oxidation on Palladium Nanocrystals with Different Types of Facets and Twin Defects Choi, Sang-Il; Herron, Jeffrey A.; Scaranto, Jessica ChemCatChem, Vol. 7, Issue 14 https://doi.org/10.1002/cctc.201500094	journal	April 2015
DFT studies on catalytic properties of isolated and carbon nanotube supported Pd9 cluster–I: adsorption, fragmentation and diffusion of hydrogen D’Anna, Vincenza; Duca, Dario; Ferrante, Francesco Physical Chemistry Chemical Physics, Vol. 11, Issue 20 https://doi.org/10.1039/b820707k	journal	January 2009
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Kinetic Isotope Effects in Complex Reaction Networks: Formic Acid Electro-Oxidation Chen, Yan-Xia; Heinen, Martin; Jusys, Zenonas ChemPhysChem, Vol. 8, Issue 3 https://doi.org/10.1002/cphc.200600520	journal	February 2007
Characterization of Boron-Nitride-Supported Pt Catalysts for the Deep Oxidation of Benzene Lin, C. Journal of Catalysis, Vol. 210, Issue 1 https://doi.org/10.1006/jcat.2002.3638	journal	August 2002
Density Functional Theory Study for Catalytic Activation and Dissociation of CO ₂ on Bimetallic Alloy Surfaces Ko, Jeonghyun; Kim, Byung-Kook; Han, Jeong Woo The Journal of Physical Chemistry C, Vol. 120, Issue 6 https://doi.org/10.1021/acs.jpcc.6b00221	journal	February 2016
Grain-size dependence of mechanical properties in polycrystalline boron-nitride: a computational study Becton, Matthew; Wang, Xianqiao Physical Chemistry Chemical Physics, Vol. 17, Issue 34 https://doi.org/10.1039/C5CP03460D	journal	January 2015
Reaction Products and Transformations of Intermediates in the Aqueous-Phase Reforming of Sorbitol Kirilin, Alexey V.; Tokarev, Anton V.; Murzina, Elena V. ChemSusChem, Vol. 3, Issue 6 https://doi.org/10.1002/cssc.200900254	journal	May 2010
Synergistic Behavior of Tubes, Junctions, and Sheets Imparts Mechano-Mutable Functionality in 3D Porous Boron Nitride Nanostructures Sakhavand, Navid; Shahsavari, Rouzbeh The Journal of Physical Chemistry C, Vol. 118, Issue 39 https://doi.org/10.1021/jp5044706	journal	July 2014
Porous boron nitride with a high surface area: hydrogen storage and water treatment Li, Jie; Lin, Jing; Xu, Xuewen Nanotechnology, Vol. 24, Issue 15, Article No. 155603 https://doi.org/10.1088/0957-4484/24/15/155603	journal	March 2013
Density functional theory studies of HCOOH decomposition on Pd(111) Scaranto, Jessica; Mavrikakis, Manos Surface Science, Vol. 650 https://doi.org/10.1016/j.susc.2015.11.020	journal	August 2016
CO ₂ Hydrogenation to Formic Acid on Ni(111) Peng, Guowen; Sibener, S. J.; Schatz, George C. The Journal of Physical Chemistry C, Vol. 116, Issue 4 https://doi.org/10.1021/jp210408x	journal	January 2012
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Synthetic routes to boron nitride Paine, Robert T.; Narula, Chaitanya K. Chemical Reviews, Vol. 90, Issue 1, p. 73-91 https://doi.org/10.1021/cr00099a004	journal	January 1990
Carbon Dioxide Conversion to Methanol over Size-Selected Cu ₄ Clusters at Low Pressures Liu, Cong; Yang, Bing; Tyo, Eric Journal of the American Chemical Society, Vol. 137, Issue 27 https://doi.org/10.1021/jacs.5b03668	journal	July 2015
Trends in Formic Acid Decomposition on Model Transition Metal Surfaces: A Density Functional Theory study Herron, Jeffrey A.; Scaranto, Jessica; Ferrin, Peter ACS Catalysis, Vol. 4, Issue 12 https://doi.org/10.1021/cs500737p	journal	November 2014
Theoretical Study of Palladium Cluster Structures on Carbonaceous Supports Duca, Dario; Ferrante, Francesco; La Manna, Gianfranco The Journal of Physical Chemistry C, Vol. 111, Issue 14 https://doi.org/10.1021/jp067167k	journal	March 2007
Binding of Pt Nanoclusters to Point Defects in Graphene: Adsorption, Morphology, and Electronic Structure Fampiou, Ioanna; Ramasubramaniam, Ashwin The Journal of Physical Chemistry C, Vol. 116, Issue 11 https://doi.org/10.1021/jp2110117	journal	March 2012
Theoretical Investigations on Decomposition of HCOOH Catalyzed by Pd ₇ Cluster Li, Song Ju; Zhou, Xin; Tian, Wei Quan The Journal of Physical Chemistry A, Vol. 116, Issue 47 https://doi.org/10.1021/jp308819j	journal	November 2012
The decomposition of formic acid on Ni(100) Benziger, J. B.; Madix, Robert J. Surface Science, Vol. 79, Issue 2 https://doi.org/10.1016/0039-6028(79)90297-8	journal	January 1979
Reactions of carboxylic acids on the Pd(111)-(2 × 2)O surface: multiple roles of surface oxygen atoms Davis, J. L.; Barteau, M. A. Surface Science, Vol. 256, Issue 1-2 https://doi.org/10.1016/0039-6028(91)91199-8	journal	October 1991
Catalysis Applications of Size-Selected Cluster Deposition Vajda, Stefan; White, Michael G. ACS Catalysis, Vol. 5, Issue 12 https://doi.org/10.1021/acscatal.5b01816	journal	November 2015
Integrated Catalytic Conversion of γ-Valerolactone to Liquid Alkenes for Transportation Fuels Bond, J. Q.; Alonso, D. M.; Wang, D. Science, Vol. 327, Issue 5969, p. 1110-1114 https://doi.org/10.1126/science.1184362	journal	February 2010
HCOOH decomposition on Pt(111): A DFT study Scaranto, Jessica; Mavrikakis, Manos Surface Science, Vol. 648 https://doi.org/10.1016/j.susc.2015.09.023	journal	June 2016
Catalytic decomposition of formic acid on Ru(001): Transient measurements Sun, Y. ‐K.; Weinberg, W. H. The Journal of Chemical Physics, Vol. 94, Issue 6 https://doi.org/10.1063/1.460587	journal	March 1991
α-d-Glucopyranose Adsorption on a Pd30 Cluster Supported on Boron Nitride Nanotube Prestianni, Antonio; Cortese, Remedios; Ferrante, Francesco Topics in Catalysis, Vol. 59, Issue 13-14 https://doi.org/10.1007/s11244-016-0638-3	journal	June 2016
Mechanistic and microkinetic analysis of CO ₂ hydrogenation on ceria Cheng, Zhuo; Lo, Cynthia S. Physical Chemistry Chemical Physics, Vol. 18, Issue 11 https://doi.org/10.1039/C5CP07469J	journal	January 2016
Hydrogen adsorption on and spillover from Au- and Cu-supported Pt3 and Pd3 clusters: a density functional study Santana, Juan A.; Rösch, Notker Physical Chemistry Chemical Physics, Vol. 14, Issue 46 https://doi.org/10.1039/c2cp43080k	journal	January 2012
Influence of adsorbate interactions on heterogeneous reaction kinetics. Formic acid decomposition on nickel Benziqer, Jay B.; Schoofs, Gregory R. The Journal of Physical Chemistry, Vol. 88, Issue 19 https://doi.org/10.1021/j150663a052	journal	September 1984
Growth of sub-nanometric palladium clusters on boron nitride nanotubes: a DFT study Schimmenti, Roberto; Cortese, Remedios; Ferrante, Francesco Physical Chemistry Chemical Physics, Vol. 18, Issue 3 https://doi.org/10.1039/C5CP06625E	journal	January 2016
DFT studies of oxidation routes for Pd9 clusters supported on γ-alumina Kacprzak, Katarzyna A.; Czekaj, Izabela; Mantzaras, John Physical Chemistry Chemical Physics, Vol. 14, Issue 29 https://doi.org/10.1039/c2cp40715a	journal	January 2012
Formic acid decomposition on Au catalysts: DFT, microkinetic modeling, and reaction kinetics experiments Singh, Suyash; Li, Sha; Carrasquillo-Flores, Ronald AIChE Journal, Vol. 60, Issue 4 https://doi.org/10.1002/aic.14401	journal	February 2014
A climbing image nudged elastic band method for finding saddle points and minimum energy paths Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904 https://doi.org/10.1063/1.1329672	journal	December 2000
On the Structure Sensitivity of Formic Acid Decomposition on Cu Catalysts Li, Sha; Scaranto, Jessica; Mavrikakis, Manos Topics in Catalysis, Vol. 59, Issue 17-18 https://doi.org/10.1007/s11244-016-0672-1	journal	August 2016
Theoretical Analysis of Transition-Metal Catalysts for Formic Acid Decomposition Yoo, Jong Suk; Abild-Pedersen, Frank; Nørskov, Jens K. ACS Catalysis, Vol. 4, Issue 4 https://doi.org/10.1021/cs400664z	journal	March 2014
H-Spillover through the Catalyst Saturation: An Ab Initio Thermodynamics Study Singh, Abhishek K.; Ribas, Morgana A.; Yakobson, Boris I. ACS Nano, Vol. 3, Issue 7 https://doi.org/10.1021/nn9004044	journal	June 2009
Competition between molecular and dissociative adsorption of hydrogen on palladium clusters deposited on defective graphene Granja, Alejandra; Alonso, Julio A.; Cabria, Iván RSC Advances, Vol. 5, Issue 59 https://doi.org/10.1039/C5RA08091F	journal	January 2015
Enhanced Nickel-Catalyzed Methanation Confined under Hexagonal Boron Nitride Shells Gao, Lijun; Fu, Qiang; Wei, Mingming ACS Catalysis, Vol. 6, Issue 10 https://doi.org/10.1021/acscatal.6b02188	journal	September 2016
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
Active oxygen on Group VIII metals: activation of formic acid and formaldehyde on Pd(100) Jorgensen, Scott W.; Madix, Robert J. Journal of the American Chemical Society, Vol. 110, Issue 2 https://doi.org/10.1021/ja00210a014	journal	January 1988
Boron Nitride Porous Microbelts for Hydrogen Storage Weng, Qunhong; Wang, Xuebin; Zhi, Chunyi ACS Nano, Vol. 7, Issue 2, p. 1558-1565 https://doi.org/10.1021/nn305320v	journal	January 2013

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

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