skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Structure Sensitivity of Formic Acid Electrooxidation on Transition Metal Surfaces: A First-Principles Study

Abstract

Formic acid presents several advantages for use as a fuel in fuel cells. We present a first-principles based analysis of electrooxidation trends for formic acid on the close-packed facets of eight fcc metals: Au, Ag, Cu, Pt, Pd, Ni, Ir, and Rh, and four hcp metals: Co, Os, Ru, and Re. To explore the structure sensitivity of this reaction on the fcc metals, we also studied the open (100) facet of these eight metals. We find that the open facets of Au, Ag, Cu, Pt, and Pd are more energy-efficient (i.e. require less overpotential) for formic acid electrooxidation when compared to their close-packed facets. The opposite is true for the stronger-binding metals: Ni, Ir, and Rh. Using the free energy of adsorbed CO* and OH* as reactivity descriptors, we cast the thermochemistry of the reaction network into phase diagrams showing regions of rate-determining steps, together with their calculated free energies. This allows the identification of bimetallic alloys, potentially possessing improved electrocatalysis for formic acid electrooxidation, compared to Pt or Pd. We discuss the need for anode catalysts for direct formic acid fuel cells (DFAFCs) to diminish CO* poisoning, by promoting the formation of formate instead of carboxyl intermediate.

Authors:
ORCiD logo [1];  [1];  [1]; ORCiD logo [1]
  1. Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemical and Biological Engineering
Publication Date:
Research Org.:
Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
OSTI Identifier:
1494744
Grant/Contract Number:  
FG02-05ER15731; AC02-06CH11357; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 165; Journal Issue: 15; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; alloys; electroxidation; formic acid

Citation Formats

Elnabawy, Ahmed O., Herron, Jeffrey A., Scaranto, Jessica, and Mavrikakis, Manos. Structure Sensitivity of Formic Acid Electrooxidation on Transition Metal Surfaces: A First-Principles Study. United States: N. p., 2018. Web. doi:10.1149/2.0161815jes.
Elnabawy, Ahmed O., Herron, Jeffrey A., Scaranto, Jessica, & Mavrikakis, Manos. Structure Sensitivity of Formic Acid Electrooxidation on Transition Metal Surfaces: A First-Principles Study. United States. doi:10.1149/2.0161815jes.
Elnabawy, Ahmed O., Herron, Jeffrey A., Scaranto, Jessica, and Mavrikakis, Manos. Sat . "Structure Sensitivity of Formic Acid Electrooxidation on Transition Metal Surfaces: A First-Principles Study". United States. doi:10.1149/2.0161815jes. https://www.osti.gov/servlets/purl/1494744.
@article{osti_1494744,
title = {Structure Sensitivity of Formic Acid Electrooxidation on Transition Metal Surfaces: A First-Principles Study},
author = {Elnabawy, Ahmed O. and Herron, Jeffrey A. and Scaranto, Jessica and Mavrikakis, Manos},
abstractNote = {Formic acid presents several advantages for use as a fuel in fuel cells. We present a first-principles based analysis of electrooxidation trends for formic acid on the close-packed facets of eight fcc metals: Au, Ag, Cu, Pt, Pd, Ni, Ir, and Rh, and four hcp metals: Co, Os, Ru, and Re. To explore the structure sensitivity of this reaction on the fcc metals, we also studied the open (100) facet of these eight metals. We find that the open facets of Au, Ag, Cu, Pt, and Pd are more energy-efficient (i.e. require less overpotential) for formic acid electrooxidation when compared to their close-packed facets. The opposite is true for the stronger-binding metals: Ni, Ir, and Rh. Using the free energy of adsorbed CO* and OH* as reactivity descriptors, we cast the thermochemistry of the reaction network into phase diagrams showing regions of rate-determining steps, together with their calculated free energies. This allows the identification of bimetallic alloys, potentially possessing improved electrocatalysis for formic acid electrooxidation, compared to Pt or Pd. We discuss the need for anode catalysts for direct formic acid fuel cells (DFAFCs) to diminish CO* poisoning, by promoting the formation of formate instead of carboxyl intermediate.},
doi = {10.1149/2.0161815jes},
journal = {Journal of the Electrochemical Society},
number = 15,
volume = 165,
place = {United States},
year = {2018},
month = {9}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Figures / Tables:

Table 1 Table 1: Free energies of key intermediates relative to HCOOH(g) at 0.00 V on close-packed and open facets of transition metals. For CO*+OH* and CO*+H2O(g), energies are given at infinite separation of involved species. For COOH*, CO*+OH* and CO*+H2O(g), stoichiometry is balanced with protons and electrons, which are not writtenmore » explicitly here. For each metal facet, among all isomeric intermediates, the most stable isomer is indicated in bold. The close-packed facet for the hcp metals Co, Os, Ru, and Re is (0001); no open facet was studied for these metals (entry --). Metals are arranged according to periodic table group in descending order and, within each group, by decreasing atomic number. The final state of CO2(g)+2(H++e-) is surfaceindependent, and is calculated to be -0.26 eV relative to HCOOH(g) at 0.00 V.« less

Save / Share:

Works referenced in this record:

Hydrogen-Evolution Catalysts Based on Non-Noble Metal Nickel-Molybdenum Nitride Nanosheets
journal, May 2012

  • Chen, Wei-Fu; Sasaki, Kotaro; Ma, Chao
  • Angewandte Chemie International Edition, Vol. 51, Issue 25
  • DOI: 10.1002/anie.201200699

Electrocatalysis of formic acid on palladium and platinum surfaces: from fundamental mechanisms to fuel cell applications
journal, January 2014

  • Jiang, Kun; Zhang, Han-Xuan; Zou, Shouzhong
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 38
  • DOI: 10.1039/C4CP03151B

Shape-directed platinum nanoparticle synthesis: nanoscale design of novel catalysts: A review of shape-directed platinum nanoparticle synthesis
journal, November 2013

  • Leong, G. Jeremy; Schulze, Maxwell C.; Strand, Matthew B.
  • Applied Organometallic Chemistry, Vol. 28, Issue 1
  • DOI: 10.1002/aoc.3048

Improving Electrocatalysts for O 2 Reduction by Fine-Tuning the Pt−Support Interaction: Pt Monolayer on the Surfaces of a Pd 3 Fe(111) Single-Crystal Alloy
journal, September 2009

  • Zhou, Wei-Ping; Yang, Xiaofang; Vukmirovic, Miomir B.
  • Journal of the American Chemical Society, Vol. 131, Issue 35
  • DOI: 10.1021/ja9039746

Electrochemical infrared studies of monocrystalline iridium surfaces Part I: Electrooxidation of formic acid and methanol
journal, September 1997


Bifunctional anode catalysts for direct methanol fuel cells
journal, January 2012

  • Rossmeisl, Jan; Ferrin, Peter; Tritsaris, Georgios A.
  • Energy & Environmental Science, Vol. 5, Issue 8
  • DOI: 10.1039/c2ee21455e

From HCOOH to CO at Pd Electrodes: A Surface-Enhanced Infrared Spectroscopy Study
journal, September 2011

  • Wang, Jin-Yi; Zhang, Han-Xuan; Jiang, Kun
  • Journal of the American Chemical Society, Vol. 133, Issue 38
  • DOI: 10.1021/ja205747j

Electrochemical Versus Heat-Engine Energy Technology: A Tribute to Wilhelm Ostwald’s Visionary Statements
journal, November 2009

  • Kunze, Julia; Stimming, Ulrich
  • Angewandte Chemie International Edition, Vol. 48, Issue 49
  • DOI: 10.1002/anie.200903603

A theoretical evaluation of possible transition metal electro-catalysts for N 2 reduction
journal, January 2012

  • Skúlason, Egill; Bligaard, Thomas; Gudmundsdóttir, Sigrídur
  • Phys. Chem. Chem. Phys., Vol. 14, Issue 3
  • DOI: 10.1039/c1cp22271f

Electrocatalytic performance of PdCo–C catalyst for formic acid oxidation
journal, October 2008


Direct synthesis of formic acid from carbon dioxide by hydrogenation in acidic media
journal, June 2014

  • Moret, Séverine; Dyson, Paul J.; Laurenczy, Gábor
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5017

Thermodynamic theory of multi-electron transfer reactions: Implications for electrocatalysis
journal, September 2011


Oxygen Reduction Reaction on Platinum-Terminated “Onion-structured” Alloy Catalysts
journal, March 2012


Theoretical Study of the Oxidation of Formic Acid on the PtAu(111) Surface in the Continuum Water Solution Phase
journal, November 2012

  • Zhong, Wenhui; Wang, Rongyue; Zhang, Dongju
  • The Journal of Physical Chemistry C, Vol. 116, Issue 45
  • DOI: 10.1021/jp307923x

On-Line FTIR Spectroscopic Investigations of Methanol Oxidation in a Direct Methanol Fuel Cell
journal, January 1997

  • Lin, W. -F.
  • Journal of The Electrochemical Society, Vol. 144, Issue 6
  • DOI: 10.1149/1.1837721

Theoretical Insight into the Trends that Guide the Electrochemical Reduction of Carbon Dioxide to Formic Acid
journal, December 2015


Simple model explaining and predicting coverage-dependent atomic adsorption energies on transition metal surfaces
journal, July 2010


Different behavior of adsorbed bridge-bonded formate from that of current in the oxidation of formic acid on platinum
journal, January 2014


Catalysts for direct formic acid fuel cells
journal, April 2003


Formic Acid Dehydrogenation on Au-Based Catalysts at Near-Ambient Temperatures
journal, June 2009

  • Ojeda, Manuel; Iglesia, Enrique
  • Angewandte Chemie International Edition, Vol. 48, Issue 26
  • DOI: 10.1002/anie.200805723

Kinetics and Mechanism of the Electrooxidation of Formic Acid—Spectroelectrochemical Studies in a Flow Cell
journal, January 2006

  • Chen, Yan Xia; Heinen, Martin; Jusys, Zenonas
  • Angewandte Chemie International Edition, Vol. 45, Issue 6
  • DOI: 10.1002/anie.200502172

Fundamental aspects of HCOOH oxidation at platinum single crystal surfaces with basal orientations and modified by irreversibly adsorbed adatoms
journal, August 2013

  • Boronat-González, A.; Herrero, E.; Feliu, J. M.
  • Journal of Solid State Electrochemistry, Vol. 18, Issue 5
  • DOI: 10.1007/s10008-013-2209-x

Adsorbed formate: the key intermediate in the oxidation of formic acid on platinum electrodes
journal, January 2011

  • Cuesta, Angel; Cabello, Gema; Gutiérrez, Claudio
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 45
  • DOI: 10.1039/c1cp22498k

Electroreduction of N 2 to Ammonia at Ambient Conditions on Mononitrides of Zr, Nb, Cr, and V: A DFT Guide for Experiments
journal, December 2015


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

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

The Brønsted–Evans–Polanyi relation and the volcano curve in heterogeneous catalysis
journal, May 2004


Reactivity descriptors for direct methanol fuel cell anode catalysts
journal, November 2008


Atomic Layer-by-Layer Deposition of Platinum on Palladium Octahedra for Enhanced Catalysts toward the Oxygen Reduction Reaction
journal, February 2015

  • Park, Jinho; Zhang, Lei; Choi, Sang-Il
  • ACS Nano, Vol. 9, Issue 3
  • DOI: 10.1021/nn506387w

PdAg Alloy Nanowires: Facile One-Step Synthesis and High Electrocatalytic Activity for Formic Acid Oxidation
journal, December 2011


Recent Development of Pd-Based Electrocatalysts for Proton Exchange Membrane Fuel Cells
journal, July 2015


Dimethyl ether electro-oxidation on platinum surfaces
journal, November 2016


Palladium–platinum core-shell icosahedra with substantially enhanced activity and durability towards oxygen reduction
journal, July 2015

  • Wang, Xue; Choi, Sang-Il; Roling, Luke T.
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8594

Ligand effects in heterogeneous catalysis and electrochemistry
journal, May 2007


Structural Effects of Electrochemical Oxidation of Formic Acid on Single Crystal Electrodes of Palladium
journal, June 2006

  • Hoshi, Nagahiro; Kida, Kaori; Nakamura, Masashi
  • The Journal of Physical Chemistry B, Vol. 110, Issue 25
  • DOI: 10.1021/jp0608372

Shape-controlled metal nanocrystals for catalytic applications
journal, August 2014

  • Ruditskiy, Aleksey; Choi, Sang-Il; Peng, Hsin-Chieh
  • MRS Bulletin, Vol. 39, Issue 8
  • DOI: 10.1557/mrs.2014.167

Recent Advances in Facile Synthesis of Bimetallic Nanostructures: An Overview
journal, January 2014

  • Dehghan Banadaki, Arash; Kajbafvala, Amir
  • Journal of Nanomaterials, Vol. 2014
  • DOI: 10.1155/2014/985948

Oxidation of formic acid on the Pt(111) surface in the gas phase
journal, January 2010

  • Gao, Wang; Keith, John A.; Anton, Josef
  • Dalton Transactions, Vol. 39, Issue 36
  • DOI: 10.1039/c0dt00404a

Reducing Pt use in the catalysts for formic acid electrooxidation via nanoengineered surface structure
journal, July 2014


Pt-Pd nanoelectrocatalyst of ultralow Pt content for the oxidation of formic acid: Towards tuning the reaction pathway
journal, May 2015


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


Why Capture CO2 from the Atmosphere?
journal, September 2009


Synthesis and Comparative Study of Nanoporous Palladium-Based Bimetallic Catalysts for Formic Acid Oxidation
journal, December 2014

  • Adams, Brian D.; Asmussen, Robert M.; Ostrom, Cassandra K.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 51
  • DOI: 10.1021/jp5095273

Electrooxidation of formic acid on gold: An ATR-SEIRAS study of the role of adsorbed formate
journal, March 2013


Catalytic and electro-catalytic oxidation of formic acid on the pure and Cu-modified Pd(111)-surface
journal, May 2008


The oxidation of formic acid at noble metal electrodes
journal, May 1973

  • Capon, Andrew; Parson, Roger
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 44, Issue 1
  • DOI: 10.1016/S0022-0728(73)80508-X

Structure Sensitivity of Methanol Electrooxidation on Transition Metals
journal, October 2009

  • Ferrin, Peter; Mavrikakis, Manos
  • Journal of the American Chemical Society, Vol. 131, Issue 40
  • DOI: 10.1021/ja904010u

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


Crossover of formic acid through Nafion® membranes
journal, May 2003


Bridge-Bonded Formate:  Active Intermediate or Spectator Species in Formic Acid Oxidation on a Pt Film Electrode?
journal, December 2006

  • Chen, Y. -X.; Heinen, M.; Jusys, Z.
  • Langmuir, Vol. 22, Issue 25
  • DOI: 10.1021/la060928q

Electrocatalytic oxidation of ethanol and ethylene glycol on cubic, octahedral and rhombic dodecahedral palladium nanocrystals
journal, January 2018

  • Ma, Xian-Yin; Chen, Yafeng; Wang, Han
  • Chemical Communications, Vol. 54, Issue 20
  • DOI: 10.1039/C7CC08793D

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

Carbon supported platinum–gold alloy catalyst for direct formic acid fuel cells
journal, December 2008


The origin of high activity of Pt–Au surfaces in the formic acid oxidation
journal, December 2009


Current Oscillations during Formic Acid Oxidation on a Pt Electrode: Insight into the Mechanism by Time-Resolved IR Spectroscopy
journal, September 2005

  • Samjeské, Gabor; Osawa, Masatoshi
  • Angewandte Chemie International Edition, Vol. 44, Issue 35
  • DOI: 10.1002/anie.200501009

Methoxy methane (dimethyl ether) as an alternative fuel for direct fuel cells
journal, June 2006


Preparation and electrochemical characterization of low-index rhodium single crystal electrodes in sulfuric acid
journal, September 2009


Theoretical Trends in Particle Size Effects for the Oxygen Reduction Reaction
journal, October 2007


The oxidation of formic acid on noble metal electrodes
journal, June 1973

  • Capon, Andrew; Parsons, Roger
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 44, Issue 2
  • DOI: 10.1016/S0022-0728(73)80250-5

Highly active and durable non-precious-metal catalysts encapsulated in carbon nanotubes for hydrogen evolution reaction
journal, January 2014

  • Deng, Jiao; Ren, Pengju; Deng, Dehui
  • Energy Environ. Sci., Vol. 7, Issue 6
  • DOI: 10.1039/C4EE00370E

Formic acid electrooxidation on Pd in acidic solutions studied by surface-enhanced infrared absorption spectroscopy
journal, January 2008

  • Miyake, Hiroto; Okada, Tatsuhiro; Samjeské, Gabor
  • Physical Chemistry Chemical Physics, Vol. 10, Issue 25
  • DOI: 10.1039/b805955a

Structural and electronic effects in heterogeneous electrocatalysis: Toward a rational design of electrocatalysts
journal, December 2013


Recent advances in direct formic acid fuel cells (DFAFC)
journal, July 2008


Direct liquid-feed fuel cells: Thermodynamic and environmental concerns
journal, June 2007


Carbon-Supported Pd−Pt Nanoalloy with Low Pt Content and Superior Catalysis for Formic Acid Electro-oxidation
journal, March 2010

  • Zhang, Han-Xuan; Wang, Chao; Wang, Jin-Yi
  • The Journal of Physical Chemistry C, Vol. 114, Issue 14
  • DOI: 10.1021/jp100835b

Towards an ammonia-mediated hydrogen economy?
journal, January 2006


First-principles computational electrochemistry: Achievements and challenges
journal, December 2012


Structural effects in electrocatalysis
journal, July 1983

  • Lamy, C.; Leger, J. M.; Clavilier, J.
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 150, Issue 1-2
  • DOI: 10.1016/S0022-0728(83)80191-0

The ensemble effect of formic acid oxidation on platinum–gold electrode studied by first-principles calculations
journal, March 2015


Core-Protected Platinum Monolayer Shell High-Stability Electrocatalysts for Fuel-Cell Cathodes
journal, October 2010

  • Sasaki, Kotaro; Naohara, Hideo; Cai, Yun
  • Angewandte Chemie International Edition, Vol. 49, Issue 46, p. 8602-8607
  • DOI: 10.1002/anie.201004287

The Priority and Challenge of High-Power Performance of Low-Platinum Proton-Exchange Membrane Fuel Cells
journal, March 2016


Electrocatalytic Oxidation of Ammonia on Transition-Metal Surfaces: A First-Principles Study
journal, February 2015

  • Herron, Jeffrey A.; Ferrin, Peter; Mavrikakis, Manos
  • The Journal of Physical Chemistry C, Vol. 119, Issue 26
  • DOI: 10.1021/jp512981f

A Comprehensive Study of Formic Acid Oxidation on Palladium Nanocrystals with Different Types of Facets and Twin Defects
journal, April 2015

  • Choi, Sang-Il; Herron, Jeffrey A.; Scaranto, Jessica
  • ChemCatChem, Vol. 7, Issue 14
  • DOI: 10.1002/cctc.201500094

Potential Oscillations in Galvanostatic Electrooxidation of Formic Acid on Platinum:  A Time-Resolved Surface-Enhanced Infrared Study
journal, December 2005

  • Samjeské, Gabor; Miki, Atsushi; Ye, Shen
  • The Journal of Physical Chemistry B, Vol. 109, Issue 49
  • DOI: 10.1021/jp055220j

Universality in Heterogeneous Catalysis
journal, July 2002

  • Nørskov, J. K.; Bligaard, T.; Logadottir, A.
  • Journal of Catalysis, Vol. 209, Issue 2
  • DOI: 10.1006/jcat.2002.3615

Near-surface alloys for hydrogen fuel cell applications
journal, January 2006


On the Structure Sensitivity of Dimethyl Ether Electro-oxidation on Eight FCC Metals: A First-Principles Study
journal, September 2015

  • Herron, Jeffrey A.; Ferrin, Peter; Mavrikakis, Manos
  • Topics in Catalysis, Vol. 58, Issue 18-20
  • DOI: 10.1007/s11244-015-0495-5

Importance of Acid–Base Equilibrium in Electrocatalytic Oxidation of Formic Acid on Platinum
journal, June 2013

  • Joo, Jiyong; Uchida, Taro; Cuesta, Angel
  • Journal of the American Chemical Society, Vol. 135, Issue 27
  • DOI: 10.1021/ja403578s

Density functional theory studies of HCOOH decomposition on Pd(111)
journal, August 2016


Electrocatalytic properties of carbon-supported Pt-Ru catalysts with the high alloying degree for formic acid electrooxidation
journal, July 2010


New insight into the CO formation mechanism during formic acid oxidation on Pt(111)
journal, December 2012


Stable ultrathin partially oxidized copper film electrode for highly efficient flexible solar cells
journal, November 2015

  • Zhao, Guoqing; Wang, Wei; Bae, Tae-Sung
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9830

Platinum monolayer electrocatalysts for oxygen reduction
journal, January 2007


In situ infrared reflectance spectroscopic study of the adsorption of formic acid at a rhodium electrode
journal, June 1986

  • Hahn, Françoise; Beden, Bernard; Lamy, Claude
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 204, Issue 1-2
  • DOI: 10.1016/0022-0728(86)80529-0

Catalyst Design by Interpolation in the Periodic Table:  Bimetallic Ammonia Synthesis Catalysts
journal, August 2001

  • Jacobsen, Claus J. H.; Dahl, Søren; Clausen, Bjerne S.
  • Journal of the American Chemical Society, Vol. 123, Issue 34
  • DOI: 10.1021/ja010963d

Hydrogen-storage materials for mobile applications
journal, November 2001

  • Schlapbach, Louis; Züttel, Andreas
  • Nature, Vol. 414, Issue 6861
  • DOI: 10.1038/35104634

Enabling electrochemical reduction of nitrogen to ammonia at ambient conditions through rational catalyst design
journal, January 2015

  • Abghoui, Younes; Garden, Anna L.; Hlynsson, Valtýr Freyr
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 7
  • DOI: 10.1039/C4CP04838E

Towards operating direct methanol fuel cells with highly concentrated fuel
journal, June 2010


PdM nanoparticles (M = Ni, Co, Fe, Mn) with high activity and stability in formic acid oxidation synthesized by sonochemical reactions
journal, September 2014


Reproducibility in density functional theory calculations of solids
journal, March 2016


Formic acid decomposition on Au catalysts: DFT, microkinetic modeling, and reaction kinetics experiments
journal, February 2014

  • Singh, Suyash; Li, Sha; Carrasquillo-Flores, Ronald
  • AIChE Journal, Vol. 60, Issue 4
  • DOI: 10.1002/aic.14401

Metal monolayer deposition by replacement of metal adlayers on electrode surfaces
journal, March 2001


First-Principles Mechanistic Analysis of Dimethyl Ether Electro-Oxidation on Monometallic Single-Crystal Surfaces
journal, September 2014

  • Herron, Jeffrey A.; Ferrin, Peter; Mavrikakis, Manos
  • The Journal of Physical Chemistry C, Vol. 118, Issue 42
  • DOI: 10.1021/jp505919x

Intermetallic Alloys as CO Electroreduction Catalysts—Role of Isolated Active Sites
journal, May 2014

  • Karamad, Mohammadreza; Tripkovic, Vladimir; Rossmeisl, Jan
  • ACS Catalysis, Vol. 4, Issue 7
  • DOI: 10.1021/cs500328c

High-temperature passive direct methanol fuel cells operating with concentrated fuels
journal, January 2015


Adsorption and electro-oxidation of carbon monoxide, methanol, ethanol and formic acid on osmium electrodeposited on glassy carbon
journal, April 2000


Tuning Reaction Rates by Lateral Strain in a Palladium Monolayer
journal, March 2005

  • Kibler, Ludwig A.; El-Aziz, Ahmed M.; Hoyer, R�diger
  • Angewandte Chemie International Edition, Vol. 44, Issue 14
  • DOI: 10.1002/anie.200462127

Electrocatalysis by foreign metal monolayers
journal, September 1978

  • Adić, Radoslav R.; Spasojević, Miroslav D.; Despić, Aleksandar R.
  • Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 92, Issue 1
  • DOI: 10.1016/S0022-0728(78)80114-4

Formic Acid Oxidation in a Polymer Electrolyte Fuel Cell
journal, January 1996

  • Weber, M.
  • Journal of The Electrochemical Society, Vol. 143, Issue 7
  • DOI: 10.1149/1.1836961

Green synthesis of PdCu supported on graphene/polyoxometalate LBL films for high-performance formic acid oxidation
journal, January 2015

  • Ma, Ai; Zhang, Xiaofeng; Wang, Xiaoying
  • RSC Advances, Vol. 5, Issue 79
  • DOI: 10.1039/C5RA09492E

The Role of Bridge-Bonded Adsorbed Formate in the Electrocatalytic Oxidation of Formic Acid on Platinum
journal, December 2010

  • Osawa, Masatoshi; Komatsu, Kei-ichi; Samjeské, Gabor
  • Angewandte Chemie International Edition, Vol. 50, Issue 5
  • DOI: 10.1002/anie.201004782

Computational chemistry for NH3 synthesis, hydrotreating, and NO reduction: Three topics of special interest to Haldor Topsøe
journal, August 2015


Composition-Dependent Electrocatalytic Activity of Pt-Cu Nanocube Catalysts for Formic Acid Oxidation
journal, January 2010

  • Xu, Dan; Bliznakov, Stoyan; Liu, Zhaoping
  • Angewandte Chemie International Edition, Vol. 49, Issue 7
  • DOI: 10.1002/anie.200905248

Electrocatalytic Oxidation of Formaldehyde on Platinum under Galvanostatic and Potential Sweep Conditions Studied by Time-Resolved Surface-Enhanced Infrared Spectroscopy
journal, September 2007

  • Samjeské,, Gabor; Miki, Atsushi; Osawa, Masatoshi
  • The Journal of Physical Chemistry C, Vol. 111, Issue 41
  • DOI: 10.1021/jp0743020

In situ infrared spectroscopic investigations of sulfate adsorption at the Ag(111) electrode surface
journal, June 1999

  • Marinković, N. S.; Marinković, J. S.; Adžić, R. R.
  • Journal of Electroanalytical Chemistry, Vol. 467, Issue 1-2
  • DOI: 10.1016/S0022-0728(99)00034-0

Electrochemical dissolution of surface alloys in acids: Thermodynamic trends from first-principles calculations
journal, May 2007


Mechanistic Study of Electrocatalytic Oxidation of Formic Acid at Platinum in Acidic Solution by Time-Resolved Surface-Enhanced Infrared Absorption Spectroscopy
journal, August 2006

  • Samjeské, Gabor; Miki, Atsushi; Ye, Shen
  • The Journal of Physical Chemistry B, Vol. 110, Issue 33
  • DOI: 10.1021/jp061891l

Electrocatalysis by design: Enhanced electrooxidation of formic acid at platinum nanoparticles–nickel oxide nanoparticles binary catalysts
journal, April 2013


Exceptional Size-Dependent Activity Enhancement in the Electroreduction of CO 2 over Au Nanoparticles
journal, November 2014

  • Mistry, Hemma; Reske, Rulle; Zeng, Zhenhua
  • Journal of the American Chemical Society, Vol. 136, Issue 47
  • DOI: 10.1021/ja508879j

Kinetic Isotope Effects in Complex Reaction Networks: Formic Acid Electro-Oxidation
journal, February 2007


Estimations of electric field effects on the oxygen reduction reaction based on the density functional theory
journal, January 2007

  • Karlberg, G. S.; Rossmeisl, J.; Nørskov, J. K.
  • Physical Chemistry Chemical Physics, Vol. 9, Issue 37
  • DOI: 10.1039/b705938h

Theoretical means for searching bimetallic alloys as anode electrocatalysts for direct liquid-feed fuel cells
journal, November 2007


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

Improved oxygen reduction reactivity of platinum monolayers on transition metal surfaces
journal, July 2008


Scaling Properties of Adsorption Energies for Hydrogen-Containing Molecules on Transition-Metal Surfaces
journal, July 2007


Mechanism of the Electrocatalytic Oxidation of Formic Acid on Metals
journal, March 2012

  • Cuesta, Angel; Cabello, Gema; Osawa, Masatoshi
  • ACS Catalysis, Vol. 2, Issue 5
  • DOI: 10.1021/cs200661z

The Challenge of Electrochemical Ammonia Synthesis: A New Perspective on the Role of Nitrogen Scaling Relations
journal, June 2015

  • Montoya, Joseph H.; Tsai, Charlie; Vojvodic, Aleksandra
  • ChemSusChem, Vol. 8, Issue 13
  • DOI: 10.1002/cssc.201500322

Insights into the Preference of CO 2 Formation from HCOOH Decomposition on Pd Surface: A Theoretical Study
journal, October 2012

  • Zhang, Riguang; Liu, Hongyan; Wang, Baojun
  • The Journal of Physical Chemistry C, Vol. 116, Issue 42
  • DOI: 10.1021/jp211900z

Tuning the Catalytic Activity of Ru@Pt Core–Shell Nanoparticles for the Oxygen Reduction Reaction by Varying the Shell Thickness
journal, January 2013

  • Yang, Lijun; Vukmirovic, Miomir B.; Su, Dong
  • The Journal of Physical Chemistry C, Vol. 117, Issue 4
  • DOI: 10.1021/jp309990e

HCOOH decomposition on Pt(111): A DFT study
journal, June 2016


Correlations in coverage-dependent atomic adsorption energies on Pd(111)
journal, May 2009


CO Adsorption Behavior on Decorated Pt@Au Nanoelectrocatalysts: A Combined Experimental and DFT Theoretical Calculation Study
journal, January 2012

  • Yu, Yaolun; Lim, Kok Hwa; Wang, Jing Yuan
  • The Journal of Physical Chemistry C, Vol. 116, Issue 5
  • DOI: 10.1021/jp210851b

Formic Acid Electrooxidation on Platinum-Group Metals:  Is Adsorbed Carbon Monoxide Solely a Catalytic Poison?
journal, October 2000

  • Mrozek, Melissa F.; Luo, Hai; Weaver, Michael J.
  • Langmuir, Vol. 16, Issue 22
  • DOI: 10.1021/la000760n

Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode
journal, November 2004

  • Nørskov, J. K.; Rossmeisl, J.; Logadottir, A.
  • The Journal of Physical Chemistry B, Vol. 108, Issue 46
  • DOI: 10.1021/jp047349j

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


Facile Synthesis of Gold-Modified Platinum Catalysts with High Performance for Formic Acid Electro-oxidation
journal, November 2014


Formic acid oxidation at palladium electrode in acidic media containing chloride anions: An in situ ATR-SEIRAS investigation
journal, September 2017


Potential Oscillations in Galvanostatic Electrooxidation of Formic Acid on Platinum:  A Mathematical Modeling and Simulation
journal, June 2006

  • Mukouyama, Yoshiharu; Kikuchi, Mitsunobu; Samjeské, Gabor
  • The Journal of Physical Chemistry B, Vol. 110, Issue 24
  • DOI: 10.1021/jp061129j

Theoretical insight on reactivity trends in CO 2 electroreduction across transition metals
journal, January 2016

  • Akhade, Sneha A.; Luo, Wenjia; Nie, Xiaowa
  • Catalysis Science & Technology, Vol. 6, Issue 4
  • DOI: 10.1039/C5CY01339A

One-Pot Synthesis of Pt-Co Alloy Nanowire Assemblies with Tunable Composition and Enhanced Electrocatalytic Properties
journal, January 2015

  • Xia, Bao Yu; Wu, Hao Bin; Li, Nan
  • Angewandte Chemie International Edition, Vol. 54, Issue 12
  • DOI: 10.1002/anie.201411544

Ultrathin AgPt alloy nanowires as a high-performance electrocatalyst for formic acid oxidation
journal, June 2017