Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Role of Hydrogen-bonded Bimolecular Formic Acid–Formate Complexes for Formic Acid Decomposition on Copper: A Combined First-Principles and Microkinetic Modeling Study

Abstract

Hydrogen bonding interactions alter the nanoscale reaction mechanisms of many chemistries. Yet, it remains unclear how they affect heterogeneously catalyzed decomposition of formic acid (FA), a reaction of intense interest since FA is a promising hydrogen carrier. In this work, we elucidate how hydrogen bonding affects the reaction mechanisms for FA decomposition on Cu(111) by combining first-principles density functional theory calculations to calculate reaction energetics, Latin-hypercube sampling to elucidate stable high-coverage adsorbate configurations, and coverage self-consistent mean-field microkinetic models to predict reaction kinetics. We demonstrate that hydrogen-bonded complexes of FA with formate (bimolecular FA–HCOO complexes) can play a dominant role in FA decomposition. Specifically, our first-principles calculations show that hydrogen bonding of FA with HCOO may stabilize the crucial monodentate HCOO intermediate and the transition states for HCOO decomposition, especially at low coverages. We predict that, depending on the reaction conditions, 40–80% of the reaction flux goes through pathways involving the bimolecular FA–HCOO complexes. Additionally, the active site for FA decomposition on Cu(111) involves a high coverage (~0.4 monolayers (ML)) of these complexes, which unexpectedly stabilize intermediates and transition states via van der Waals interactions. Our work provides molecular insights consistent with previous experimental observations on supported Cu/Al2O3 catalysts. Thismore » paves the way toward the development of novel catalysts for FA decomposition as well as for other industrially important chemistries with intermediates capable of hydrogen bonding, such as ammonia electrooxidation and CO2 hydrogenation.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. Univ. of Wisconsin, Madison, WI (United States)
Publication Date:
Research Org.:
Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1835133
Grant/Contract Number:  
FG02-05ER15731; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 11; Journal Issue: 7; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; copper; hydrogen bonding; cocatalyst; formic acid decomposition; bimolecular mechanism; microkinetic modeling; density functional theory; coverage effects

Citation Formats

Chen, Benjamin J., Bhandari, Saurabh, and Mavrikakis, Manos. Role of Hydrogen-bonded Bimolecular Formic Acid–Formate Complexes for Formic Acid Decomposition on Copper: A Combined First-Principles and Microkinetic Modeling Study. United States: N. p., 2021. Web. doi:10.1021/acscatal.0c05695.
Copy to clipboard
Chen, Benjamin J., Bhandari, Saurabh, & Mavrikakis, Manos. Role of Hydrogen-bonded Bimolecular Formic Acid–Formate Complexes for Formic Acid Decomposition on Copper: A Combined First-Principles and Microkinetic Modeling Study. United States. https://doi.org/10.1021/acscatal.0c05695
Copy to clipboard
Chen, Benjamin J., Bhandari, Saurabh, and Mavrikakis, Manos. Wed . "Role of Hydrogen-bonded Bimolecular Formic Acid–Formate Complexes for Formic Acid Decomposition on Copper: A Combined First-Principles and Microkinetic Modeling Study". United States. https://doi.org/10.1021/acscatal.0c05695. https://www.osti.gov/servlets/purl/1835133.
Copy to clipboard
@article{osti_1835133,
title = {Role of Hydrogen-bonded Bimolecular Formic Acid–Formate Complexes for Formic Acid Decomposition on Copper: A Combined First-Principles and Microkinetic Modeling Study},
author = {Chen, Benjamin J. and Bhandari, Saurabh and Mavrikakis, Manos},
abstractNote = {Hydrogen bonding interactions alter the nanoscale reaction mechanisms of many chemistries. Yet, it remains unclear how they affect heterogeneously catalyzed decomposition of formic acid (FA), a reaction of intense interest since FA is a promising hydrogen carrier. In this work, we elucidate how hydrogen bonding affects the reaction mechanisms for FA decomposition on Cu(111) by combining first-principles density functional theory calculations to calculate reaction energetics, Latin-hypercube sampling to elucidate stable high-coverage adsorbate configurations, and coverage self-consistent mean-field microkinetic models to predict reaction kinetics. We demonstrate that hydrogen-bonded complexes of FA with formate (bimolecular FA–HCOO complexes) can play a dominant role in FA decomposition. Specifically, our first-principles calculations show that hydrogen bonding of FA with HCOO may stabilize the crucial monodentate HCOO intermediate and the transition states for HCOO decomposition, especially at low coverages. We predict that, depending on the reaction conditions, 40–80% of the reaction flux goes through pathways involving the bimolecular FA–HCOO complexes. Additionally, the active site for FA decomposition on Cu(111) involves a high coverage (~0.4 monolayers (ML)) of these complexes, which unexpectedly stabilize intermediates and transition states via van der Waals interactions. Our work provides molecular insights consistent with previous experimental observations on supported Cu/Al2O3 catalysts. This paves the way toward the development of novel catalysts for FA decomposition as well as for other industrially important chemistries with intermediates capable of hydrogen bonding, such as ammonia electrooxidation and CO2 hydrogenation.},
doi = {10.1021/acscatal.0c05695},
journal = {ACS Catalysis},
number = 7,
volume = 11,
place = {United States},
year = {Wed Mar 24 00:00:00 EDT 2021},
month = {Wed Mar 24 00:00:00 EDT 2021}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acscatal.0c05695
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Unimolecular and bimolecular formic acid decomposition on copper
journal, October 1986

  • Iglesia, Enrique
  • The Journal of Physical Chemistry, Vol. 90, Issue 21
  • DOI: 10.1021/j100412a074

Biomass oxidation to formic acid in aqueous media using polyoxometalate catalysts – boosting FA selectivity by in-situ extraction
journal, January 2015

  • Reichert, Jenny; Brunner, Birgit; Jess, Andreas
  • Energy & Environmental Science, Vol. 8, Issue 10
  • DOI: 10.1039/C5EE01706H

Projector augmented-wave method
journal, December 1994

Hydrogen-Bonding Catalysis and Inhibition by Simple Solvents in the Stereoselective Kinetic Epoxide-Opening Spirocyclization of Glycal Epoxides to Form Spiroketals
journal, May 2011

  • Wurst, Jacqueline M.; Liu, Guodong; Tan, Derek S.
  • Journal of the American Chemical Society, Vol. 133, Issue 20
  • DOI: 10.1021/ja201249c

Asymmetric Catalysis by Chiral Hydrogen-Bond Donors
journal, February 2006

  • Taylor, Mark S.; Jacobsen, Eric N.
  • Angewandte Chemie International Edition, Vol. 45, Issue 10
  • DOI: 10.1002/anie.200503132

Atom-Resolved Imaging of Dynamic Shape Changes in Supported Copper Nanocrystals
journal, March 2002

Multiple Bonding Configurations of Adsorbed Formate on Ag{111}
journal, January 1996

  • Sim, W. S.; Gardner, P.; King, D. A.
  • The Journal of Physical Chemistry, Vol. 100, Issue 30
  • DOI: 10.1021/jp9600726

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Future Directions and Industrial Perspectives Micro- and macro-kinetics: Their relationship in heterogeneous catalysis
journal, September 1994

Assisted deprotonation of formic acid on Cu(111) and self-assembly of 1D chains
journal, January 2013

  • Baber, Ashleigh E.; Mudiyanselage, Kumudu; Senanayake, Sanjaya D.
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 29
  • DOI: 10.1039/c3cp51533h

Periodic boundary conditions in ab initio calculations
journal, February 1995

Reaction Mechanism of Vapor-Phase Formic Acid Decomposition over Platinum Catalysts: DFT, Reaction Kinetics Experiments, and Microkinetic Modeling
journal, March 2020

  • Bhandari, Saurabh; Rangarajan, Srinivas; Maravelias, Christos T.
  • ACS Catalysis, Vol. 10, Issue 7
  • DOI: 10.1021/acscatal.9b05424

A benchmark database for adsorption bond energies to transition metal surfaces and comparison to selected DFT functionals
journal, October 2015

Combining Computational Modeling with Reaction Kinetics Experiments for Elucidating the In Situ Nature of the Active Site in Catalysis
journal, September 2020

  • Bhandari, Saurabh; Rangarajan, Srinivas; Mavrikakis, Manos
  • Accounts of Chemical Research, Vol. 53, Issue 9
  • DOI: 10.1021/acs.accounts.0c00340

Synergistic Catalysis of Metal–Organic Framework-Immobilized Au–Pd Nanoparticles in Dehydrogenation of Formic Acid for Chemical Hydrogen Storage
journal, August 2011

  • Gu, Xiaojun; Lu, Zhang-Hui; Jiang, Hai-Long
  • Journal of the American Chemical Society, Vol. 133, Issue 31
  • DOI: 10.1021/ja200122f

Sequential-Optimization-Based Framework for Robust Modeling and Design of Heterogeneous Catalytic Systems
journal, November 2017

  • Rangarajan, Srinivas; Maravelias, Christos T.; Mavrikakis, Manos
  • The Journal of Physical Chemistry C, Vol. 121, Issue 46
  • DOI: 10.1021/acs.jpcc.7b08089

New insights into the kinetics of formic acid decomposition on copper surfaces
journal, July 1986

A self-adjusting platinum surface for acetone hydrogenation
journal, January 2020

  • Demir, Benginur; Kropp, Thomas; Rivera-Dones, Keishla R.
  • Proceedings of the National Academy of Sciences, Vol. 117, Issue 7
  • DOI: 10.1073/pnas.1917110117

Large Sample Properties of Simulations Using Latin Hypercube Sampling
journal, May 1987

Small-Molecule H-Bond Donors in Asymmetric Catalysis
journal, December 2007

  • Doyle, Abigail G.; Jacobsen, Eric N.
  • Chemical Reviews, Vol. 107, Issue 12
  • DOI: 10.1021/cr068373r

Structure- and Coverage-Sensitive Mechanism of NO Reduction on Platinum Electrodes
journal, June 2017

  • Katsounaros, Ioannis; Figueiredo, Marta C.; Chen, Xiaoting
  • ACS Catalysis, Vol. 7, Issue 7
  • DOI: 10.1021/acscatal.7b01069

A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000

  • Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
  • DOI: 10.1063/1.1329672

Density functional theory in surface chemistry and catalysis
journal, January 2011

  • Norskov, J. K.; Abild-Pedersen, F.; Studt, F.
  • Proceedings of the National Academy of Sciences, Vol. 108, Issue 3
  • DOI: 10.1073/pnas.1006652108

High-precision sampling for Brillouin-zone integration in metals
journal, August 1989

Formic Acid as a Hydrogen Energy Carrier
journal, December 2016

Theoretical Analysis of Transition-Metal Catalysts for Formic Acid Decomposition
journal, March 2014

  • Yoo, Jong Suk; Abild-Pedersen, Frank; Nørskov, Jens K.
  • ACS Catalysis, Vol. 4, Issue 4
  • DOI: 10.1021/cs400664z

Dimers of formic acid: Structures, stability, and double proton transfer
journal, July 2017

  • Farfán, Paola; Echeverri, Andrea; Diaz, Estefanía
  • The Journal of Chemical Physics, Vol. 147, Issue 4
  • DOI: 10.1063/1.4985880

Icosahedral nanocrystals of noble metals: Synthesis and applications
journal, August 2017

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

Selective Hydrogen Production from Formic Acid Decomposition on Pd–Au Bimetallic Surfaces
journal, July 2014

  • Yu, Wen-Yueh; Mullen, Gregory M.; Flaherty, David W.
  • Journal of the American Chemical Society, Vol. 136, Issue 31
  • DOI: 10.1021/ja505192v

What makes zeolitic imidazolate frameworks hydrophobic or hydrophilic? The impact of geometry and functionalization on water adsorption
journal, January 2014

  • Ortiz, Aurélie U.; Freitas, Alexy P.; Boutin, Anne
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 21
  • DOI: 10.1039/C3CP54292K

Comparison of Three Methods for Selecting Values of Input Variables in the Analysis of Output from a Computer Code
journal, May 1979

Formic Acid: A Hydrogen-Bonding Cocatalyst for Formate Decomposition
journal, August 2020

Density Functional Theory Calculations and Analysis of Reaction Pathways for Reduction of Nitric Oxide by Hydrogen on Pt(111)
journal, September 2014

  • Farberow, Carrie A.; Dumesic, James A.; Mavrikakis, Manos
  • ACS Catalysis, Vol. 4, Issue 10
  • DOI: 10.1021/cs500668k

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996

Decomposition mechanism of formic acid on Cu (111) surface: A theoretical study
journal, February 2017

Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

Theoretical Elucidation of the Competitive Electro-oxidation Mechanisms of Formic Acid on Pt(111)
journal, December 2010

  • Gao, Wang; Keith, John A.; Anton, Josef
  • Journal of the American Chemical Society, Vol. 132, Issue 51
  • DOI: 10.1021/ja1083317

Thermal desorption study of formic acid decomposition on a clean Cu(110) surface
journal, January 1980

Catalytic Dehydrogenation of Formic Acid on Metallic Catalysts
journal, September 1959

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996

Density-Functional Analysis of Hydrogen on Pt(111): Electric Field, Solvent, and Coverage Effects
journal, June 2008

  • Hamada, Ikutaro; Morikawa, Yoshitada
  • The Journal of Physical Chemistry C, Vol. 112, Issue 29
  • DOI: 10.1021/jp8028787

Microscopic View of the Active Sites for Selective Dehydrogenation of Formic Acid on Cu(111)
journal, November 2015

  • Marcinkowski, Matthew D.; Murphy, Colin J.; Liriano, Melissa L.
  • ACS Catalysis, Vol. 5, Issue 12
  • DOI: 10.1021/acscatal.5b01994

Trends in Formic Acid Decomposition on Model Transition Metal Surfaces: A Density Functional Theory study
journal, November 2014

  • Herron, Jeffrey A.; Scaranto, Jessica; Ferrin, Peter
  • ACS Catalysis, Vol. 4, Issue 12
  • DOI: 10.1021/cs500737p

Dense CO Adlayers as Enablers of CO Hydrogenation Turnovers on Ru Surfaces
journal, August 2017

  • Liu, Jianwei; Hibbitts, David; Iglesia, Enrique
  • Journal of the American Chemical Society, Vol. 139, Issue 34
  • DOI: 10.1021/jacs.7b04606

Structure Sensitivity of Formic Acid Electrooxidation on Transition Metal Surfaces: A First-Principles Study
journal, January 2018

  • Elnabawy, Ahmed O.; Herron, Jeffrey A.; Scaranto, Jessica
  • Journal of The Electrochemical Society, Vol. 165, Issue 15
  • DOI: 10.1149/2.0161815jes

CO Chemisorption and Dissociation at High Coverages during CO Hydrogenation on Ru Catalysts
journal, April 2013

  • Loveless, Brett T.; Buda, Corneliu; Neurock, Matthew
  • Journal of the American Chemical Society, Vol. 135, Issue 16
  • DOI: 10.1021/ja311848e

Metal–Organic Frameworks for Separations
journal, September 2011

  • Li, Jian-Rong; Sculley, Julian; Zhou, Hong-Cai
  • Chemical Reviews, Vol. 112, Issue 2, p. 869-932
  • DOI: 10.1021/cr200190s

Van der Waals density functional study of formic acid adsorption and decomposition on Cu(111)
journal, April 2019

  • Putra, Septia Eka Marsha; Muttaqien, Fahdzi; Hamamoto, Yuji
  • The Journal of Chemical Physics, Vol. 150, Issue 15
  • DOI: 10.1063/1.5087420

Adsorption measurements during surface catalysis. The decomposition of formic acid on a copper catalyst
journal, January 1959

Adsorbate-substrate and adsorbate-adsorbate interactions of Na and K adlayers on Al(111)
journal, December 1992

On the Structure Sensitivity of Formic Acid Decomposition on Cu Catalysts
journal, August 2016

Hydrogen production from formic acid decomposition at room temperature using a Ag–Pd core–shell nanocatalyst
journal, April 2011

  • Tedsree, Karaked; Li, Tong; Jones, Simon
  • Nature Nanotechnology, Vol. 6, Issue 5
  • DOI: 10.1038/nnano.2011.42

Kinetic Monte Carlo simulations of heterogeneously catalyzed oxidation reactions
journal, January 2014

  • Hess, Franziska; Over, Herbert
  • Catal. Sci. Technol., Vol. 4, Issue 3
  • DOI: 10.1039/C3CY00833A

Efficient Subnanometric Gold-Catalyzed Hydrogen Generation via Formic Acid Decomposition under Ambient Conditions
journal, May 2012

  • Bi, Qing-Yuan; Du, Xian-Long; Liu, Yong-Mei
  • Journal of the American Chemical Society, Vol. 134, Issue 21
  • DOI: 10.1021/ja301696e

SBH10: A Benchmark Database of Barrier Heights on Transition Metal Surfaces
journal, September 2017

  • Mallikarjun Sharada, Shaama; Bligaard, Thomas; Luntz, Alan C.
  • The Journal of Physical Chemistry C, Vol. 121, Issue 36
  • DOI: 10.1021/acs.jpcc.7b05677

Revisiting formic acid decomposition on metallic powder catalysts: Exploding the HCOOH decomposition volcano curve
journal, August 2016

Mechanism of Methanol Synthesis on Cu through CO 2 and CO Hydrogenation
journal, February 2011

  • Grabow, L. C.; Mavrikakis, M.
  • ACS Catalysis, Vol. 1, Issue 4
  • DOI: 10.1021/cs200055d
    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: