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

Elnabawy, Ahmed O.; Herron, Jeffrey A.; Scaranto, Jessica; Mavrikakis, Manos

doi:10.1149/2.0161815jes

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

Journal Article · 22 September 2018 · Journal of the Electrochemical Society

DOI: https://doi.org/10.1149/2.0161815jes · OSTI ID:1494744

^[1]; Herron, Jeffrey A. ^[1]; Scaranto, Jessica ^[1];

^[1]

Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemical and Biological Engineering

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.

View Accepted Manuscript (DOE)

Cite

Export

Save

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: FG02-05ER15731; AC02-06CH11357; AC02-05CH11231

OSTI ID:: 1494744

Journal Information:: Journal of the Electrochemical Society, Vol. 165, Issue 15; ISSN 0013-4651

Publisher:: The Electrochemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (149)

Hydrogen-Evolution Catalysts Based on Non-Noble Metal Nickel-Molybdenum Nitride Nanosheets Chen, Wei-Fu; Sasaki, Kotaro; Ma, Chao Angewandte Chemie International Edition, Vol. 51, Issue 25 https://doi.org/10.1002/anie.201200699	journal	May 2012
Formic acid oxidation reaction on a PdxNiy bimetallic nanoparticle catalyst prepared by a thermal decomposition process using ionic liquids as the solvent Ding, Keqiang; Liu, Lu; Cao, Yanli International Journal of Hydrogen Energy, Vol. 39, Issue 14 https://doi.org/10.1016/j.ijhydene.2014.03.026	journal	May 2014
Electrocatalysis of formic acid on palladium and platinum surfaces: from fundamental mechanisms to fuel cell applications Jiang, Kun; Zhang, Han-Xuan; Zou, Shouzhong Phys. Chem. Chem. Phys., Vol. 16, Issue 38 https://doi.org/10.1039/C4CP03151B	journal	January 2014
Shape-directed platinum nanoparticle synthesis: nanoscale design of novel catalysts: A review of shape-directed platinum nanoparticle synthesis Leong, G. Jeremy; Schulze, Maxwell C.; Strand, Matthew B. Applied Organometallic Chemistry, Vol. 28, Issue 1 https://doi.org/10.1002/aoc.3048	journal	November 2013
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 Zhou, Wei-Ping; Yang, Xiaofang; Vukmirovic, Miomir B. Journal of the American Chemical Society, Vol. 131, Issue 35 https://doi.org/10.1021/ja9039746	journal	September 2009
Electrochemical infrared studies of monocrystalline iridium surfaces Part I: Electrooxidation of formic acid and methanol Gómez, Roberto; Weaver, Michael J. Journal of Electroanalytical Chemistry, Vol. 435, Issue 1-2 https://doi.org/10.1016/S0022-0728(97)00304-5	journal	September 1997
Bifunctional anode catalysts for direct methanol fuel cells Rossmeisl, Jan; Ferrin, Peter; Tritsaris, Georgios A. Energy & Environmental Science, Vol. 5, Issue 8 https://doi.org/10.1039/c2ee21455e	journal	January 2012
From HCOOH to CO at Pd Electrodes: A Surface-Enhanced Infrared Spectroscopy Study Wang, Jin-Yi; Zhang, Han-Xuan; Jiang, Kun Journal of the American Chemical Society, Vol. 133, Issue 38 https://doi.org/10.1021/ja205747j	journal	September 2011
Electrochemical Versus Heat-Engine Energy Technology: A Tribute to Wilhelm Ostwaldâ€™s Visionary Statements Kunze, Julia; Stimming, Ulrich Angewandte Chemie International Edition, Vol. 48, Issue 49 https://doi.org/10.1002/anie.200903603	journal	November 2009
A theoretical evaluation of possible transition metal electro-catalysts for N ₂ reduction Skúlason, Egill; Bligaard, Thomas; Gudmundsdóttir, Sigrídur Phys. Chem. Chem. Phys., Vol. 14, Issue 3 https://doi.org/10.1039/c1cp22271f	journal	January 2012
Electrocatalytic performance of PdCo–C catalyst for formic acid oxidation Wang, Xiaoming; Xia, Yongyao Electrochemistry Communications, Vol. 10, Issue 10 https://doi.org/10.1016/j.elecom.2008.08.043	journal	October 2008
Direct synthesis of formic acid from carbon dioxide by hydrogenation in acidic media Moret, Séverine; Dyson, Paul J.; Laurenczy, Gábor Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5017	journal	June 2014
Thermodynamic theory of multi-electron transfer reactions: Implications for electrocatalysis Koper, Marc T. M. Journal of Electroanalytical Chemistry, Vol. 660, Issue 2 https://doi.org/10.1016/j.jelechem.2010.10.004	journal	September 2011
Oxygen Reduction Reaction on Platinum-Terminated “Onion-structured” Alloy Catalysts Herron, Jeffrey A.; Jiao, Jiao; Hahn, Konstanze Electrocatalysis, Vol. 3, Issue 3-4 https://doi.org/10.1007/s12678-012-0087-0	journal	March 2012
Theoretical Study of the Oxidation of Formic Acid on the PtAu(111) Surface in the Continuum Water Solution Phase Zhong, Wenhui; Wang, Rongyue; Zhang, Dongju The Journal of Physical Chemistry C, Vol. 116, Issue 45 https://doi.org/10.1021/jp307923x	journal	November 2012
On-Line FTIR Spectroscopic Investigations of Methanol Oxidation in a Direct Methanol Fuel Cell Lin, W. -F. Journal of The Electrochemical Society, Vol. 144, Issue 6 https://doi.org/10.1149/1.1837721	journal	January 1997
Theoretical Insight into the Trends that Guide the Electrochemical Reduction of Carbon Dioxide to Formic Acid Yoo, Jong Suk; Christensen, Rune; Vegge, Tejs ChemSusChem, Vol. 9, Issue 4 https://doi.org/10.1002/cssc.201501197	journal	December 2015
Simple model explaining and predicting coverage-dependent atomic adsorption energies on transition metal surfaces İnoğlu, Nilay; Kitchin, John R. Physical Review B, Vol. 82, Issue 4 https://doi.org/10.1103/PhysRevB.82.045414	journal	July 2010
Different behavior of adsorbed bridge-bonded formate from that of current in the oxidation of formic acid on platinum Okamoto, Hiroshi; Numata, Yukimasa; Gojuki, Takeshi Electrochimica Acta, Vol. 116 https://doi.org/10.1016/j.electacta.2013.11.053	journal	January 2014
Catalysts for direct formic acid fuel cells Rice, C. Journal of Power Sources, Vol. 115, Issue 2 https://doi.org/10.1016/S0378-7753(03)00026-0	journal	April 2003
Formic Acid Dehydrogenation on Au-Based Catalysts at Near-Ambient Temperatures Ojeda, Manuel; Iglesia, Enrique Angewandte Chemie International Edition, Vol. 48, Issue 26 https://doi.org/10.1002/anie.200805723	journal	June 2009
Kinetics and Mechanism of the Electrooxidation of Formic Acid—Spectroelectrochemical Studies in a Flow Cell Chen, Yan Xia; Heinen, Martin; Jusys, Zenonas Angewandte Chemie International Edition, Vol. 45, Issue 6 https://doi.org/10.1002/anie.200502172	journal	January 2006
Fundamental aspects of HCOOH oxidation at platinum single crystal surfaces with basal orientations and modified by irreversibly adsorbed adatoms Boronat-González, A.; Herrero, E.; Feliu, J. M. Journal of Solid State Electrochemistry, Vol. 18, Issue 5 https://doi.org/10.1007/s10008-013-2209-x	journal	August 2013
Adsorbed formate: the key intermediate in the oxidation of formic acid on platinum electrodes Cuesta, Angel; Cabello, Gema; Gutiérrez, Claudio Physical Chemistry Chemical Physics, Vol. 13, Issue 45 https://doi.org/10.1039/c1cp22498k	journal	January 2011
Electroreduction of N ₂ to Ammonia at Ambient Conditions on Mononitrides of Zr, Nb, Cr, and V: A DFT Guide for Experiments Abghoui, Younes; Garden, Anna L.; Howalt, Jakob G. ACS Catalysis, Vol. 6, Issue 2 https://doi.org/10.1021/acscatal.5b01918	journal	December 2015
Density functional theory in surface chemistry and catalysis Norskov, J. K.; Abild-Pedersen, F.; Studt, F. Proceedings of the National Academy of Sciences, Vol. 108, Issue 3 https://doi.org/10.1073/pnas.1006652108	journal	January 2011
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
The Brønsted–Evans–Polanyi relation and the volcano curve in heterogeneous catalysis Bligaard, T.; Nørskov, J. K.; Dahl, S. Journal of Catalysis, Vol. 224, Issue 1 https://doi.org/10.1016/j.jcat.2004.02.034	journal	May 2004
Reactivity descriptors for direct methanol fuel cell anode catalysts Ferrin, Peter; Nilekar, Anand Udaykumar; Greeley, Jeff Surface Science, Vol. 602, Issue 21 https://doi.org/10.1016/j.susc.2008.08.011	journal	November 2008
Atomic Layer-by-Layer Deposition of Pt on Pd Nanocubes for Catalysts with Enhanced Activity and Durability toward Oxygen Reduction Xie, Shuifen; Choi, Sang-Il; Lu, Ning Nano Letters, Vol. 14, Issue 6 https://doi.org/10.1021/nl501205j	journal	May 2014
Atomic Layer-by-Layer Deposition of Platinum on Palladium Octahedra for Enhanced Catalysts toward the Oxygen Reduction Reaction Park, Jinho; Zhang, Lei; Choi, Sang-Il ACS Nano, Vol. 9, Issue 3 https://doi.org/10.1021/nn506387w	journal	February 2015
PdAg Alloy Nanowires: Facile One-Step Synthesis and High Electrocatalytic Activity for Formic Acid Oxidation Lu, Yizhong; Chen, Wei ACS Catalysis, Vol. 2, Issue 1 https://doi.org/10.1021/cs200538g	journal	December 2011
Recent Development of Pd-Based Electrocatalysts for Proton Exchange Membrane Fuel Cells Meng, Hui; Zeng, Dongrong; Xie, Fangyan Catalysts, Vol. 5, Issue 3 https://doi.org/10.3390/catal5031221	journal	July 2015
Dimethyl ether electro-oxidation on platinum surfaces Roling, Luke T.; Herron, Jeffrey A.; Budiman, Winny Nano Energy, Vol. 29 https://doi.org/10.1016/j.nanoen.2016.02.041	journal	November 2016
Palladium–platinum core-shell icosahedra with substantially enhanced activity and durability towards oxygen reduction Wang, Xue; Choi, Sang-Il; Roling, Luke T. Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8594	journal	July 2015
Ligand effects in heterogeneous catalysis and electrochemistry Bligaard, T.; Nørskov, J. K. Electrochimica Acta, Vol. 52, Issue 18 https://doi.org/10.1016/j.electacta.2007.02.041	journal	May 2007
Structural Effects of Electrochemical Oxidation of Formic Acid on Single Crystal Electrodes of Palladium Hoshi, Nagahiro; Kida, Kaori; Nakamura, Masashi The Journal of Physical Chemistry B, Vol. 110, Issue 25 https://doi.org/10.1021/jp0608372	journal	June 2006
Shape-controlled metal nanocrystals for catalytic applications Ruditskiy, Aleksey; Choi, Sang-Il; Peng, Hsin-Chieh MRS Bulletin, Vol. 39, Issue 8 https://doi.org/10.1557/mrs.2014.167	journal	August 2014
Recent Advances in Facile Synthesis of Bimetallic Nanostructures: An Overview Dehghan Banadaki, Arash; Kajbafvala, Amir Journal of Nanomaterials, Vol. 2014 https://doi.org/10.1155/2014/985948	journal	January 2014
Oxidation of formic acid on the Pt(111) surface in the gas phase Gao, Wang; Keith, John A.; Anton, Josef Dalton Transactions, Vol. 39, Issue 36 https://doi.org/10.1039/c0dt00404a	journal	January 2010
Reducing Pt use in the catalysts for formic acid electrooxidation via nanoengineered surface structure Liao, Mengyin; Wang, Yulu; Chen, Guoqin Journal of Power Sources, Vol. 257 https://doi.org/10.1016/j.jpowsour.2014.01.103	journal	July 2014
Pt-Pd nanoelectrocatalyst of ultralow Pt content for the oxidation of formic acid: Towards tuning the reaction pathway Ghosh, Sourov; Raj, C. Retna Journal of Chemical Sciences, Vol. 127, Issue 5 https://doi.org/10.1007/s12039-015-0854-6	journal	May 2015
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
Why Capture CO2 from the Atmosphere? Keith, D. W. Science, Vol. 325, Issue 5948 https://doi.org/10.1126/science.1175680	journal	September 2009
Synthesis and Comparative Study of Nanoporous Palladium-Based Bimetallic Catalysts for Formic Acid Oxidation Adams, Brian D.; Asmussen, Robert M.; Ostrom, Cassandra K. The Journal of Physical Chemistry C, Vol. 118, Issue 51 https://doi.org/10.1021/jp5095273	journal	December 2014
Electrooxidation of formic acid on gold: An ATR-SEIRAS study of the role of adsorbed formate Cuesta, Angel; Cabello, Gema; Hartl, Fabian W. Catalysis Today, Vol. 202 https://doi.org/10.1016/j.cattod.2012.04.022	journal	March 2013
Catalytic and electro-catalytic oxidation of formic acid on the pure and Cu-modified Pd(111)-surface Brandt, K.; Steinhausen, M.; Wandelt, K. Journal of Electroanalytical Chemistry, Vol. 616, Issue 1-2 https://doi.org/10.1016/j.jelechem.2007.12.015	journal	May 2008
The oxidation of formic acid at noble metal electrodes Capon, Andrew; Parson, Roger Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 44, Issue 1 https://doi.org/10.1016/S0022-0728(73)80508-X	journal	May 1973
Structure Sensitivity of Methanol Electrooxidation on Transition Metals Ferrin, Peter; Mavrikakis, Manos Journal of the American Chemical Society, Vol. 131, Issue 40 https://doi.org/10.1021/ja904010u	journal	October 2009
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
Crossover of formic acid through Nafion® membranes Rhee, Young-Woo; Ha, Su Y.; Masel, Richard I. Journal of Power Sources, Vol. 117, Issue 1-2 https://doi.org/10.1016/S0378-7753(03)00352-5	journal	May 2003
Bridge-Bonded Formate: Active Intermediate or Spectator Species in Formic Acid Oxidation on a Pt Film Electrode? ^† Chen, Y. -X.; Heinen, M.; Jusys, Z. Langmuir, Vol. 22, Issue 25 https://doi.org/10.1021/la060928q	journal	December 2006
Electrocatalytic oxidation of ethanol and ethylene glycol on cubic, octahedral and rhombic dodecahedral palladium nanocrystals Ma, Xian-Yin; Chen, Yafeng; Wang, Han Chemical Communications, Vol. 54, Issue 20 https://doi.org/10.1039/C7CC08793D	journal	January 2018
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
Carbon supported platinum–gold alloy catalyst for direct formic acid fuel cells Xu, J. B.; Zhao, T. S.; Liang, Z. X. Journal of Power Sources, Vol. 185, Issue 2 https://doi.org/10.1016/j.jpowsour.2008.09.039	journal	December 2008
The origin of high activity of Pt–Au surfaces in the formic acid oxidation Obradović, Maja D.; Tripković, Amalija V.; Gojković, Snežana Lj. Electrochimica Acta, Vol. 55, Issue 1 https://doi.org/10.1016/j.electacta.2009.08.038	journal	December 2009
Current Oscillations during Formic Acid Oxidation on a Pt Electrode: Insight into the Mechanism by Time-Resolved IR Spectroscopy Samjeské, Gabor; Osawa, Masatoshi Angewandte Chemie International Edition, Vol. 44, Issue 35 https://doi.org/10.1002/anie.200501009	journal	September 2005
Methoxy methane (dimethyl ether) as an alternative fuel for direct fuel cells Kerangueven, G.; Coutanceau, C.; Sibert, E. Journal of Power Sources, Vol. 157, Issue 1 https://doi.org/10.1016/j.jpowsour.2005.07.080	journal	June 2006
Preparation and electrochemical characterization of low-index rhodium single crystal electrodes in sulfuric acid Xu, Qinqin; Linke, Udo; Bujak, Renata Electrochimica Acta, Vol. 54, Issue 23 https://doi.org/10.1016/j.electacta.2009.04.061	journal	September 2009
Theoretical Trends in Particle Size Effects for the Oxygen Reduction Reaction Greeley, J.; Rossmeisl, J.; Hellmann, A. Zeitschrift für Physikalische Chemie, Vol. 221, Issue 9-10 https://doi.org/10.1524/zpch.2007.221.9-10.1209	journal	October 2007
The oxidation of formic acid on noble metal electrodes Capon, Andrew; Parsons, Roger Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 44, Issue 2 https://doi.org/10.1016/S0022-0728(73)80250-5	journal	June 1973
Highly active and durable non-precious-metal catalysts encapsulated in carbon nanotubes for hydrogen evolution reaction Deng, Jiao; Ren, Pengju; Deng, Dehui Energy Environ. Sci., Vol. 7, Issue 6 https://doi.org/10.1039/C4EE00370E	journal	January 2014
Formic acid electrooxidation on Pd in acidic solutions studied by surface-enhanced infrared absorption spectroscopy Miyake, Hiroto; Okada, Tatsuhiro; Samjeské, Gabor Physical Chemistry Chemical Physics, Vol. 10, Issue 25 https://doi.org/10.1039/b805955a	journal	January 2008
Structural and electronic effects in heterogeneous electrocatalysis: Toward a rational design of electrocatalysts Bandarenka, Aliaksandr S.; Koper, Marc T. M. Journal of Catalysis, Vol. 308 https://doi.org/10.1016/j.jcat.2013.05.006	journal	December 2013
Recent advances in direct formic acid fuel cells (DFAFC) Yu, Xingwen; Pickup, Peter G. Journal of Power Sources, Vol. 182, Issue 1, p. 124-132 https://doi.org/10.1016/j.jpowsour.2008.03.075	journal	July 2008
Direct liquid-feed fuel cells: Thermodynamic and environmental concerns Demirci, Umit B. Journal of Power Sources, Vol. 169, Issue 2 https://doi.org/10.1016/j.jpowsour.2007.03.050	journal	June 2007
Carbon-Supported Pd−Pt Nanoalloy with Low Pt Content and Superior Catalysis for Formic Acid Electro-oxidation Zhang, Han-Xuan; Wang, Chao; Wang, Jin-Yi The Journal of Physical Chemistry C, Vol. 114, Issue 14 https://doi.org/10.1021/jp100835b	journal	March 2010
Towards an ammonia-mediated hydrogen economy? Christensen, Claus Hviid; Johannessen, Tue; Sørensen, Rasmus Zink Catalysis Today, Vol. 111, Issue 1-2 https://doi.org/10.1016/j.cattod.2005.10.011	journal	January 2006
First-principles computational electrochemistry: Achievements and challenges Calle-Vallejo, Federico; Koper, Marc T. M. Electrochimica Acta, Vol. 84 https://doi.org/10.1016/j.electacta.2012.04.062	journal	December 2012
Structural effects in electrocatalysis Lamy, C.; Leger, J. M.; Clavilier, J. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 150, Issue 1-2 https://doi.org/10.1016/S0022-0728(83)80191-0	journal	July 1983
The electrodeposition of rhenium species at the sub-monolayer level on a platinum electrode and its effect on formic acid electrooxidation Schrebler, R.; Gómez, H.; Córdova, R. Electrochimica Acta, Vol. 34, Issue 10 https://doi.org/10.1016/0013-4686(89)87179-8	journal	October 1989
The ensemble effect of formic acid oxidation on platinum–gold electrode studied by first-principles calculations Zhong, Wenhui; Qi, Yuanyuan; Deng, Mingsen Journal of Power Sources, Vol. 278 https://doi.org/10.1016/j.jpowsour.2014.12.071	journal	March 2015
Core-Protected Platinum Monolayer Shell High-Stability Electrocatalysts for Fuel-Cell Cathodes Sasaki, Kotaro; Naohara, Hideo; Cai, Yun Angewandte Chemie International Edition, Vol. 49, Issue 46, p. 8602-8607 https://doi.org/10.1002/anie.201004287	journal	October 2010
Application of In-situ Attenuated Total Reflection-Fourier Transform Infrared Spectroscopy for the Understanding of Complex Reaction Mechanism and Kinetics: Formic Acid Oxidation on a Pt Film Electrode at Elevated Temperatures Chen, Yan Xia; Ye, Shen; Heinen, Martin The Journal of Physical Chemistry B, Vol. 110, Issue 19 https://doi.org/10.1021/jp057463h	journal	May 2006
The Priority and Challenge of High-Power Performance of Low-Platinum Proton-Exchange Membrane Fuel Cells Kongkanand, Anusorn; Mathias, Mark F. The Journal of Physical Chemistry Letters, Vol. 7, Issue 7 https://doi.org/10.1021/acs.jpclett.6b00216	journal	March 2016
Electrocatalytic Oxidation of Ammonia on Transition-Metal Surfaces: A First-Principles Study Herron, Jeffrey A.; Ferrin, Peter; Mavrikakis, Manos The Journal of Physical Chemistry C, Vol. 119, Issue 26 https://doi.org/10.1021/jp512981f	journal	February 2015
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
Composition-Dependent Electrocatalytic Activity of Palladium–Iridium Binary Alloy Nanoparticles Supported on the Multiwalled Carbon Nanotubes for the Electro-Oxidation of Formic Acid Bao, Jianming; Dou, Meiling; Liu, Haijing ACS Applied Materials & Interfaces, Vol. 7, Issue 28 https://doi.org/10.1021/acsami.5b01848	journal	July 2015
Potential Oscillations in Galvanostatic Electrooxidation of Formic Acid on Platinum: A Time-Resolved Surface-Enhanced Infrared Study Samjeské, Gabor; Miki, Atsushi; Ye, Shen The Journal of Physical Chemistry B, Vol. 109, Issue 49 https://doi.org/10.1021/jp055220j	journal	December 2005
Ultrasonic-assisted synthesis of Pd–Ni alloy catalysts supported on multi-walled carbon nanotubes for formic acid electrooxidation Li, Ruoshi; Wei, Zhen; Huang, Tao Electrochimica Acta, Vol. 56, Issue 19 https://doi.org/10.1016/j.electacta.2011.05.097	journal	July 2011
Universality in Heterogeneous Catalysis Nørskov, J. K.; Bligaard, T.; Logadottir, A. Journal of Catalysis, Vol. 209, Issue 2 https://doi.org/10.1006/jcat.2002.3615	journal	July 2002
Near-surface alloys for hydrogen fuel cell applications Greeley, Jeff; Mavrikakis, Manos Catalysis Today, Vol. 111, Issue 1-2, p. 52-58 https://doi.org/10.1016/j.cattod.2005.10.009	journal	January 2006
On the Structure Sensitivity of Dimethyl Ether Electro-oxidation on Eight FCC Metals: A First-Principles Study Herron, Jeffrey A.; Ferrin, Peter; Mavrikakis, Manos Topics in Catalysis, Vol. 58, Issue 18-20 https://doi.org/10.1007/s11244-015-0495-5	journal	September 2015
Importance of Acid–Base Equilibrium in Electrocatalytic Oxidation of Formic Acid on Platinum Joo, Jiyong; Uchida, Taro; Cuesta, Angel Journal of the American Chemical Society, Vol. 135, Issue 27 https://doi.org/10.1021/ja403578s	journal	June 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
Electrocatalytic properties of carbon-supported Pt-Ru catalysts with the high alloying degree for formic acid electrooxidation Chen, Yu; Zhou, Yiming; Tang, Yawen Journal of Power Sources, Vol. 195, Issue 13 https://doi.org/10.1016/j.jpowsour.2010.01.054	journal	July 2010
New insight into the CO formation mechanism during formic acid oxidation on Pt(111) Zhong, Wenhui; Zhang, Dongju Catalysis Communications, Vol. 29 https://doi.org/10.1016/j.catcom.2012.09.002	journal	December 2012
Infrared spectroscopic study of methanol and formic acid absorbates on a platinum electrode: Part II. Role of the linear CO(a) derived from methanol and formic acid in the electrocatalytic oxidation of CH₃OH and HCOOH Kunimatsu, K.; Kita, H. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 218, Issue 1-2, p. 155-172 https://doi.org/10.1016/0022-0728(87)87013-4	journal	February 1987
Stable ultrathin partially oxidized copper film electrode for highly efficient flexible solar cells Zhao, Guoqing; Wang, Wei; Bae, Tae-Sung Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms9830	journal	November 2015
Platinum monolayer electrocatalysts for oxygen reduction Vukmirovic, M. B.; Zhang, J.; Sasaki, K. Electrochimica Acta, Vol. 52, Issue 6 https://doi.org/10.1016/j.electacta.2006.05.062	journal	January 2007
In situ infrared reflectance spectroscopic study of the adsorption of formic acid at a rhodium electrode Hahn, Françoise; Beden, Bernard; Lamy, Claude Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 204, Issue 1-2 https://doi.org/10.1016/0022-0728(86)80529-0	journal	June 1986
Catalyst Design by Interpolation in the Periodic Table: Bimetallic Ammonia Synthesis Catalysts Jacobsen, Claus J. H.; Dahl, Søren; Clausen, Bjerne S. Journal of the American Chemical Society, Vol. 123, Issue 34 https://doi.org/10.1021/ja010963d	journal	August 2001
Hydrogen-storage materials for mobile applications Schlapbach, Louis; Züttel, Andreas Nature, Vol. 414, Issue 6861 https://doi.org/10.1038/35104634	journal	November 2001
Enabling electrochemical reduction of nitrogen to ammonia at ambient conditions through rational catalyst design Abghoui, Younes; Garden, Anna L.; Hlynsson, Valtýr Freyr Physical Chemistry Chemical Physics, Vol. 17, Issue 7 https://doi.org/10.1039/C4CP04838E	journal	January 2015
Towards operating direct methanol fuel cells with highly concentrated fuel Zhao, T. S.; Yang, W. W.; Chen, R. Journal of Power Sources, Vol. 195, Issue 11 https://doi.org/10.1016/j.jpowsour.2009.11.140	journal	June 2010
PdM nanoparticles (M = Ni, Co, Fe, Mn) with high activity and stability in formic acid oxidation synthesized by sonochemical reactions Matin, Md. Abdul; Jang, Ji-Hoon; Kwon, Young-Uk Journal of Power Sources, Vol. 262 https://doi.org/10.1016/j.jpowsour.2014.03.109	journal	September 2014
Reproducibility in density functional theory calculations of solids Lejaeghere, K.; Bihlmayer, G.; Bjorkman, T. Science, Vol. 351, Issue 6280 https://doi.org/10.1126/science.aad3000	journal	March 2016
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
Metal monolayer deposition by replacement of metal adlayers on electrode surfaces Brankovic, S. R.; Wang, J. X.; Adžić, R. R. Surface Science, Vol. 474, Issue 1-3, p. L173-L179 https://doi.org/10.1016/S0039-6028(00)01103-1	journal	March 2001
First-Principles Mechanistic Analysis of Dimethyl Ether Electro-Oxidation on Monometallic Single-Crystal Surfaces Herron, Jeffrey A.; Ferrin, Peter; Mavrikakis, Manos The Journal of Physical Chemistry C, Vol. 118, Issue 42 https://doi.org/10.1021/jp505919x	journal	September 2014
Intermetallic Alloys as CO Electroreduction Catalysts—Role of Isolated Active Sites Karamad, Mohammadreza; Tripkovic, Vladimir; Rossmeisl, Jan ACS Catalysis, Vol. 4, Issue 7 https://doi.org/10.1021/cs500328c	journal	May 2014
High-temperature passive direct methanol fuel cells operating with concentrated fuels Zhao, Xuxin; Yuan, Wenxiang; Wu, Qixing Journal of Power Sources, Vol. 273 https://doi.org/10.1016/j.jpowsour.2014.09.128	journal	January 2015
Adsorption and electro-oxidation of carbon monoxide, methanol, ethanol and formic acid on osmium electrodeposited on glassy carbon Orozco, G.; Gutiérrez, C. Journal of Electroanalytical Chemistry, Vol. 484, Issue 1 https://doi.org/10.1016/S0022-0728(00)00062-0	journal	April 2000
Tuning Reaction Rates by Lateral Strain in a Palladium Monolayer Kibler, Ludwig A.; El-Aziz, Ahmed M.; Hoyer, R�diger Angewandte Chemie International Edition, Vol. 44, Issue 14 https://doi.org/10.1002/anie.200462127	journal	March 2005
Electrocatalysis by foreign metal monolayers Adić, Radoslav R.; Spasojević, Miroslav D.; Despić, Aleksandar R. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 92, Issue 1 https://doi.org/10.1016/S0022-0728(78)80114-4	journal	September 1978
Formic Acid Oxidation in a Polymer Electrolyte Fuel Cell Weber, M. Journal of The Electrochemical Society, Vol. 143, Issue 7 https://doi.org/10.1149/1.1836961	journal	January 1996
Green synthesis of PdCu supported on graphene/polyoxometalate LBL films for high-performance formic acid oxidation Ma, Ai; Zhang, Xiaofeng; Wang, Xiaoying RSC Advances, Vol. 5, Issue 79 https://doi.org/10.1039/C5RA09492E	journal	January 2015
The Role of Bridge-Bonded Adsorbed Formate in the Electrocatalytic Oxidation of Formic Acid on Platinum Osawa, Masatoshi; Komatsu, Kei-ichi; Samjeské, Gabor Angewandte Chemie International Edition, Vol. 50, Issue 5 https://doi.org/10.1002/anie.201004782	journal	December 2010
Computational chemistry for NH3 synthesis, hydrotreating, and NO reduction: Three topics of special interest to Haldor Topsøe Elnabawy, Ahmed O.; Rangarajan, Srinivas; Mavrikakis, Manos Journal of Catalysis, Vol. 328 https://doi.org/10.1016/j.jcat.2014.12.018	journal	August 2015
Composition-Dependent Electrocatalytic Activity of Pt-Cu Nanocube Catalysts for Formic Acid Oxidation Xu, Dan; Bliznakov, Stoyan; Liu, Zhaoping Angewandte Chemie International Edition, Vol. 49, Issue 7 https://doi.org/10.1002/anie.200905248	journal	January 2010
Electrocatalytic Oxidation of Formaldehyde on Platinum under Galvanostatic and Potential Sweep Conditions Studied by Time-Resolved Surface-Enhanced Infrared Spectroscopy Samjeské,, Gabor; Miki, Atsushi; Osawa, Masatoshi The Journal of Physical Chemistry C, Vol. 111, Issue 41 https://doi.org/10.1021/jp0743020	journal	September 2007
In situ infrared spectroscopic investigations of sulfate adsorption at the Ag(111) electrode surface Marinković, N. S.; Marinković, J. S.; Adžić, R. R. Journal of Electroanalytical Chemistry, Vol. 467, Issue 1-2 https://doi.org/10.1016/S0022-0728(99)00034-0	journal	June 1999
Electrochemical dissolution of surface alloys in acids: Thermodynamic trends from first-principles calculations Greeley, J.; Nørskov, J. K. Electrochimica Acta, Vol. 52, Issue 19 https://doi.org/10.1016/j.electacta.2007.02.082	journal	May 2007
Mechanistic Study of Electrocatalytic Oxidation of Formic Acid at Platinum in Acidic Solution by Time-Resolved Surface-Enhanced Infrared Absorption Spectroscopy Samjeské, Gabor; Miki, Atsushi; Ye, Shen The Journal of Physical Chemistry B, Vol. 110, Issue 33 https://doi.org/10.1021/jp061891l	journal	August 2006
Electrocatalysis by design: Enhanced electrooxidation of formic acid at platinum nanoparticles–nickel oxide nanoparticles binary catalysts El-Nagar, Gumaa A.; Mohammad, Ahmad M.; El-Deab, Mohamed S. Electrochimica Acta, Vol. 94 https://doi.org/10.1016/j.electacta.2013.01.133	journal	April 2013
Exceptional Size-Dependent Activity Enhancement in the Electroreduction of CO ₂ over Au Nanoparticles Mistry, Hemma; Reske, Rulle; Zeng, Zhenhua Journal of the American Chemical Society, Vol. 136, Issue 47 https://doi.org/10.1021/ja508879j	journal	November 2014
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
Estimations of electric field effects on the oxygen reduction reaction based on the density functional theory Karlberg, G. S.; Rossmeisl, J.; Nørskov, J. K. Physical Chemistry Chemical Physics, Vol. 9, Issue 37 https://doi.org/10.1039/b705938h	journal	January 2007
Theoretical means for searching bimetallic alloys as anode electrocatalysts for direct liquid-feed fuel cells Demirci, Umit B. Journal of Power Sources, Vol. 173, Issue 1 https://doi.org/10.1016/j.jpowsour.2007.04.069	journal	November 2007
Theoretical Elucidation of the Competitive Electro-oxidation Mechanisms of Formic Acid on Pt(111) Gao, Wang; Keith, John A.; Anton, Josef Journal of the American Chemical Society, Vol. 132, Issue 51 https://doi.org/10.1021/ja1083317	journal	December 2010
Improved oxygen reduction reactivity of platinum monolayers on transition metal surfaces Nilekar, Anand Udaykumar; Mavrikakis, Manos Surface Science, Vol. 602, Issue 14 https://doi.org/10.1016/j.susc.2008.05.036	journal	July 2008
Scaling Properties of Adsorption Energies for Hydrogen-Containing Molecules on Transition-Metal Surfaces Abild-Pedersen, F.; Greeley, J.; Studt, F. Physical Review Letters, Vol. 99, Issue 1 https://doi.org/10.1103/PhysRevLett.99.016105	journal	July 2007
Mechanism of the Electrocatalytic Oxidation of Formic Acid on Metals Cuesta, Angel; Cabello, Gema; Osawa, Masatoshi ACS Catalysis, Vol. 2, Issue 5 https://doi.org/10.1021/cs200661z	journal	March 2012
The Challenge of Electrochemical Ammonia Synthesis: A New Perspective on the Role of Nitrogen Scaling Relations Montoya, Joseph H.; Tsai, Charlie; Vojvodic, Aleksandra ChemSusChem, Vol. 8, Issue 13 https://doi.org/10.1002/cssc.201500322	journal	June 2015
Formic acid oxidation on platinum: a simple mechanistic study Schwarz, Kathleen A.; Sundararaman, Ravishankar; Moffat, Thomas P. Physical Chemistry Chemical Physics, Vol. 17, Issue 32 https://doi.org/10.1039/C5CP03045E	journal	January 2015
Insights into the Preference of CO ₂ Formation from HCOOH Decomposition on Pd Surface: A Theoretical Study Zhang, Riguang; Liu, Hongyan; Wang, Baojun The Journal of Physical Chemistry C, Vol. 116, Issue 42 https://doi.org/10.1021/jp211900z	journal	October 2012
Tuning the Catalytic Activity of Ru@Pt Core–Shell Nanoparticles for the Oxygen Reduction Reaction by Varying the Shell Thickness Yang, Lijun; Vukmirovic, Miomir B.; Su, Dong The Journal of Physical Chemistry C, Vol. 117, Issue 4 https://doi.org/10.1021/jp309990e	journal	January 2013
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
Correlations in coverage-dependent atomic adsorption energies on Pd(111) Kitchin, John R. Physical Review B, Vol. 79, Issue 20 https://doi.org/10.1103/PhysRevB.79.205412	journal	May 2009
CO Adsorption Behavior on Decorated Pt@Au Nanoelectrocatalysts: A Combined Experimental and DFT Theoretical Calculation Study Yu, Yaolun; Lim, Kok Hwa; Wang, Jing Yuan The Journal of Physical Chemistry C, Vol. 116, Issue 5 https://doi.org/10.1021/jp210851b	journal	January 2012
Formic Acid Electrooxidation on Platinum-Group Metals: Is Adsorbed Carbon Monoxide Solely a Catalytic Poison? Mrozek, Melissa F.; Luo, Hai; Weaver, Michael J. Langmuir, Vol. 16, Issue 22 https://doi.org/10.1021/la000760n	journal	October 2000
Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode Nørskov, J. K.; Rossmeisl, J.; Logadottir, A. The Journal of Physical Chemistry B, Vol. 108, Issue 46 https://doi.org/10.1021/jp047349j	journal	November 2004
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
Facile Synthesis of Gold-Modified Platinum Catalysts with High Performance for Formic Acid Electro-oxidation Zhang, Ke; Ren, Fangfang; Wang, Huiwen ChemPlusChem, Vol. 80, Issue 3 https://doi.org/10.1002/cplu.201402231	journal	November 2014
Formic acid oxidation at palladium electrode in acidic media containing chloride anions: An in situ ATR-SEIRAS investigation Jiang, Kun; Wang, Jin-Yi; Zhao, Ting-Ting Journal of Electroanalytical Chemistry, Vol. 800 https://doi.org/10.1016/j.jelechem.2016.12.021	journal	September 2017
Potential Oscillations in Galvanostatic Electrooxidation of Formic Acid on Platinum: A Mathematical Modeling and Simulation Mukouyama, Yoshiharu; Kikuchi, Mitsunobu; Samjeské, Gabor The Journal of Physical Chemistry B, Vol. 110, Issue 24 https://doi.org/10.1021/jp061129j	journal	June 2006
Theoretical insight on reactivity trends in CO ₂ electroreduction across transition metals Akhade, Sneha A.; Luo, Wenjia; Nie, Xiaowa Catalysis Science & Technology, Vol. 6, Issue 4 https://doi.org/10.1039/C5CY01339A	journal	January 2016
One-Pot Synthesis of Pt-Co Alloy Nanowire Assemblies with Tunable Composition and Enhanced Electrocatalytic Properties Xia, Bao Yu; Wu, Hao Bin; Li, Nan Angewandte Chemie International Edition, Vol. 54, Issue 12 https://doi.org/10.1002/anie.201411544	journal	January 2015
Ultrathin AgPt alloy nanowires as a high-performance electrocatalyst for formic acid oxidation Jiang, Xian; Fu, Gengtao; Wu, Xia Nano Research, Vol. 11, Issue 1 https://doi.org/10.1007/s12274-017-1658-4	journal	June 2017
The Role of Bridge-Bonded Adsorbed Formate in the Electrocatalytic Oxidation of Formic Acid on Platinum Osawa, Masatoshi; Komatsu, Kei-ichi; Samjeské, Gabor Angewandte Chemie, Vol. 123, Issue 5 https://doi.org/10.1002/ange.201004782	journal	December 2010
Hydrogen-Evolution Catalysts Based on Non-Noble Metal Nickel-Molybdenum Nitride Nanosheets Chen, Wei-Fu; Sasaki, Kotaro; Ma, Chao Angewandte Chemie, Vol. 124, Issue 25 https://doi.org/10.1002/ange.201200699	journal	May 2012
1D Pd-Based Nanomaterials as Efficient Electrocatalysts for Fuel Cells Lu, Yizhong; Chen, Wei Green Energy and Technology https://doi.org/10.1007/978-1-4471-6473-9_12	book	January 2014
One-Pot Synthesis of Pt-Co Alloy Nanowire Assemblies with Tunable Composition and Enhanced Electrocatalytic Properties Xia, Bao Yu; Wu, Hao Bin; Li, Nan Angewandte Chemie, Vol. 127, Issue 12 https://doi.org/10.1002/ange.201411544	journal	February 2015
Structural effects in electrocatalysis Popović, K. Dj.; Marković, N. M.; Tripković, A. V. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 313, Issue 1-2 https://doi.org/10.1016/0022-0728(91)85179-s	journal	September 1991
High-resolution X-ray luminescence extension imaging Ou, Xiangyu; Qin, Xian; Huang, Bolong Nature, Vol. 590, Issue 7846 https://doi.org/10.1038/s41586-021-03251-6	journal	February 2021
Current Oscillations during Formic Acid Oxidation on a Pt Electrode: Insight into the Mechanism by Time-Resolved IR Spectroscopy Samjeské, Gabor; Osawa, Masatoshi Angewandte Chemie, Vol. 117, Issue 35 https://doi.org/10.1002/ange.200501009	journal	September 2005
Hydrogen-storage materials for mobile applications Schlapbach, Louis; Züttel, Andreas Materials for Sustainable Energy https://doi.org/10.1142/9789814317665_0038	book	October 2010
Structural effects in electrocatalysis Marković, N. M.; Avramov-Ivić, M. L.; Marinković, N. S. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 312, Issue 1-2 https://doi.org/10.1016/0022-0728(91)85147-h	journal	August 1991
Composition-Dependent Electrocatalytic Activity of Pt-Cu Nanocube Catalysts for Formic Acid Oxidation Xu, Dan; Bliznakov, Stoyan; Liu, Zhaoping Angewandte Chemie, Vol. 122, Issue 7 https://doi.org/10.1002/ange.200905248	journal	February 2010

Cited By (3)

Towards more active and stable PdAgCr electrocatalysts for formic acid electrooxidation: The role of optimization via response surface methodology Ulas, Berdan; Caglar, Aykut; Yılmaz, Sakir International Journal of Energy Research, Vol. 43, Issue 15 https://doi.org/10.1002/er.4880	journal	September 2019
Electrocatalytic Activities towards the Electrochemical Oxidation of Formic Acid and Oxygen Reduction Reactions over Bimetallic, Trimetallic and Core–Shell-Structured Pd-Based Materials Gunji, Takao; Matsumoto, Futoshi Inorganics, Vol. 7, Issue 3 https://doi.org/10.3390/inorganics7030036	journal	March 2019
Determination of optimum Pd:Ni ratio for Pd _x Ni _{100‐ x} / CNT s formic acid electrooxidation catalysts synthesized via sodium borohydride reduction method Ulas, Berdan; Caglar, Aykut; Kivrak, Hilal International Journal of Energy Research, Vol. 43, Issue 8 https://doi.org/10.1002/er.4485	journal	March 2019