Probing the Effects of Acid Electrolyte Anions on Electrocatalyst Activity and Selectivity for the Oxygen Reduction Reaction

Zamora Zeledón, José A.; Kamat, Gaurav Ashish; Gunasooriya, G. Kalhara; Nørskov, Jens K.; Stevens, Michaela Burke; Jaramillo, Thomas F.

doi:10.1002/celc.202100500

Probing the Effects of Acid Electrolyte Anions on Electrocatalyst Activity and Selectivity for the Oxygen Reduction Reaction

Journal Article · Thu Jul 01 00:00:00 EDT 2021 · ChemElectroChem

DOI:https://doi.org/10.1002/celc.202100500· OSTI ID:1817874

^[1]; ^[1]; ^[2]; ^[2]; ^[1]; ^[1]

Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis; Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Technical Univ. of Denmark, Lyngby (Denmark). Catalysis Theory Center

The local microenvironment at the electrode-electrolyte interface plays an important role in electrocatalytic performance. Herein, we investigate the effect of acid electrolyte anion identity on the oxygen reduction reaction (ORR) activity and selectivity of smooth Ag and Pd catalyst thin films. Cyclic voltammetry in perchloric, nitric, sulfuric, phosphoric, hydrochloric, and hydrobromic acid, at pH1, reveals that Ag ORR activity trends as follows: HClO₄>HNO₃>H₂SO₄>H₃PO₄>HCl>>HBr, while Pd ORR activity trends as: HClO₄>H₂SO₄>HNO₃>H₃PO₄>HCl>>HBr. Moreover, rotating-ring-disk-electrode selectivity measurements demonstrate enhanced 4e^- selectivity on both Ag and Pd, by up to 35% H₂O₂ and 10% H₂O₂ respectively, in HNO₃ compared to in HClO₄. Relating physics-based modeling and experimental results, we postulate that ORR performance depends greatly on anion-related phenomena in the double layer, for instance competitive adsorption and non-covalent interactions.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: National Science Foundation (NSF); Toyota Research Institute; USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1817874

Alternate ID(s):: OSTI ID: 1808618

Journal Information:: ChemElectroChem, Journal Name: ChemElectroChem Journal Issue: 13 Vol. 8; ISSN 2196-0216

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

References (72)

Ions in Solution and their Solvation Marcus, Yizhak https://doi.org/10.1002/9781118892336	book	June 2015
Effect of Electrolyte Concentration on the Stern Layer Thickness at a Charged Interface Brown, Matthew A.; Goel, Alok; Abbas, Zareen Angewandte Chemie, Vol. 128, Issue 11 https://doi.org/10.1002/ange.201512025	journal	February 2016
Effect of Electrolyte Concentration on the Stern Layer Thickness at a Charged Interface Brown, Matthew A.; Goel, Alok; Abbas, Zareen Angewandte Chemie International Edition, Vol. 55, Issue 11 https://doi.org/10.1002/anie.201512025	journal	February 2016
Oxygen Reduction Reaction on Silver Catalysts in Alkaline Media: a Minireview Erikson, Heiki; Sarapuu, Ave; Tammeveski, Kaido ChemElectroChem, Vol. 6, Issue 1 https://doi.org/10.1002/celc.201800913	journal	October 2018
Outer Helmholtz Plane of the Electrical Double Layer Formed at the Solid Electrode-Liquid Interface Nakamura, Masashi; Sato, Narumasa; Hoshi, Nagahiro ChemPhysChem, Vol. 12, Issue 8 https://doi.org/10.1002/cphc.201100011	journal	February 2011
The Effect of Anions and pH on the Activity and Selectivity of an Annealed Polycrystalline Au Film Electrode in the Oxygen Reduction Reaction‐Revisited Jusys, Zenonas; Behm, R. Jürgen ChemPhysChem, Vol. 20, Issue 24 https://doi.org/10.1002/cphc.201900960	journal	November 2019
Bond formation in electrosorbates—I correlation between the electrosorption valency and pauling's electronegativity for aqueous solutions Schultze, J. W.; Koppitz, F. D. Electrochimica Acta, Vol. 21, Issue 5 https://doi.org/10.1016/0013-4686(76)85022-0	journal	May 1976
Bond formation in electrosorbates—II electrosorption and double layer properties in non-aqueous solvents Koppitz, F. D.; Schultze, J. W. Electrochimica Acta, Vol. 21, Issue 5 https://doi.org/10.1016/0013-4686(76)85023-2	journal	May 1976
Electrolyte effects on oxygen reduction kinetics at platinum: A rotating ring-disc electrode analysis Hsueh, K-L.; Gonzalez, E. R.; Srinivasan, S. Electrochimica Acta, Vol. 28, Issue 5 https://doi.org/10.1016/0013-4686(83)85066-X	journal	May 1983
Elementary steps of electrochemical oxidation of single-crystal planes of Au—I. Chemical basis of processes involving geometry of anions and the electrode surfaces Angerstein-Kozlowska, H.; Conway, B. E.; Hamelin, A. Electrochimica Acta, Vol. 31, Issue 8 https://doi.org/10.1016/0013-4686(86)80020-2	journal	August 1986
Electrochemical surface science: The study of monolayers of ad-atoms and solvent molecules at charged metal interfaces Conway, B. Progress in Surface Science, Vol. 16, Issue 1 https://doi.org/10.1016/0079-6816(84)90008-X	journal	January 1984
Electrochemistry and environment: The role of electrocatalysis*1 Trasatti, S. International Journal of Hydrogen Energy, Vol. 20, Issue 10 https://doi.org/10.1016/0360-3199(95)00014-5	journal	October 1995
The oxygen reduction reaction on a Pt/carbon fuel cell catalyst in the presence of chloride anions Schmidt, T. J.; Paulus, U. A.; Gasteiger, H. A. Journal of Electroanalytical Chemistry, Vol. 508, Issue 1-2 https://doi.org/10.1016/S0022-0728(01)00499-5	journal	July 2001
A study of the dissolution of platinum, palladium, rhodium and gold electrodes in 1 m sulphuric acid by cyclic voltammetry Rand, D. A. J.; Woods, R. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 35, Issue 1 https://doi.org/10.1016/S0022-0728(72)80308-5	journal	March 1972
Oxygen reduction reaction on Pt(111): effects of bromide Marković, N. M.; Gasteiger, H. A.; Grgur, B. N. Journal of Electroanalytical Chemistry, Vol. 467, Issue 1-2 https://doi.org/10.1016/S0022-0728(99)00020-0	journal	June 1999
Determination of oxygen solubility in aqueous sulphuric acid media Kaskiala, T. Minerals Engineering, Vol. 15, Issue 11 https://doi.org/10.1016/S0892-6875(02)00089-4	journal	November 2002
Cyclic voltammetry on Ag(111) and Ag(100) faces in sodium hydroxide solutions Jovic, B. M.; Jovic, V. D.; Stafford, G. R. Electrochemistry Communications, Vol. 1, Issue 6 https://doi.org/10.1016/S1388-2481(99)00049-1	journal	June 1999
The adsorption of bisulfate and sulfate anions over a Pt(111) electrode: A first principle study of adsorption configurations, vibrational frequencies and linear sweep voltammogram simulations Yeh, Kuan-Yu; Restaino, Nicholas A.; Esopi, Monica R. Catalysis Today, Vol. 202 https://doi.org/10.1016/j.cattod.2012.03.011	journal	March 2013
Theoretical and mechanistic aspects of proton-coupled electron transfer in electrochemistry Costentin, Cyrille; Savéant, Jean-Michel Current Opinion in Electrochemistry, Vol. 1, Issue 1 https://doi.org/10.1016/j.coelec.2016.11.001	journal	February 2017
Recent progress on first-principles simulations of voltammograms Li, Yawei; Janik, Michael J. Current Opinion in Electrochemistry, Vol. 14 https://doi.org/10.1016/j.coelec.2019.01.005	journal	April 2019
Enhanced electrocatalytic activity of cubic Pd nanoparticles towards the oxygen reduction reaction in acid media Erikson, Heiki; Sarapuu, Ave; Tammeveski, Kaido Electrochemistry Communications, Vol. 13, Issue 7 https://doi.org/10.1016/j.elecom.2011.04.024	journal	July 2011
Oxygen electroreduction on Ag(111): The pH effect Blizanac, B. B.; Ross, P. N.; Markovic, N. M. Electrochimica Acta, Vol. 52, Issue 6 https://doi.org/10.1016/j.electacta.2006.06.047	journal	January 2007
Electrochemical behaviour of palladium electrode: Oxidation, electrodissolution and ionic adsorption Grdeń, Michal; Łukaszewski, Mariusz; Jerkiewicz, Gregory Electrochimica Acta, Vol. 53, Issue 26 https://doi.org/10.1016/j.electacta.2008.05.046	journal	November 2008
Electroreduction of oxygen on gold-supported nanostructured palladium films in acid solutions Sarapuu, Ave; Kasikov, Aarne; Wong, Naomi Electrochimica Acta, Vol. 55, Issue 22 https://doi.org/10.1016/j.electacta.2010.05.092	journal	September 2010
Electrochemical reduction of oxygen on palladium nanocubes in acid and alkaline solutions Erikson, H.; Sarapuu, A.; Alexeyeva, N. Electrochimica Acta, Vol. 59 https://doi.org/10.1016/j.electacta.2011.10.074	journal	January 2012
Evaluation of temperature and electrolyte concentration dependent Oxygen solubility and diffusivity in phosphoric acid Fleige, Michael; Holst-Olesen, Kaspar; Wiberg, Gustav Karl Henrik Electrochimica Acta, Vol. 209 https://doi.org/10.1016/j.electacta.2016.05.048	journal	August 2016
Hydrogen and halide co-adsorption on Pt(111) in an electrochemical environment: a computational perspective Gossenberger, Florian; Roman, Tanglaw; Groß, Axel Electrochimica Acta, Vol. 216 https://doi.org/10.1016/j.electacta.2016.08.117	journal	October 2016
Oxygen reduction reaction on thin-film Ag electrodes in alkaline solution Linge, Jonas Mart; Erikson, Heiki; Kasikov, Aarne Electrochimica Acta, Vol. 325 https://doi.org/10.1016/j.electacta.2019.134922	journal	December 2019
Impacts of anions on the electrochemical oxygen reduction reaction activity and stability of Pt/C in alkaline electrolyte You, Gaoping; Zhu, Wei; Zhuang, Zhongbin International Journal of Hydrogen Energy, Vol. 44, Issue 26 https://doi.org/10.1016/j.ijhydene.2019.03.264	journal	May 2019
Oxygen reduction on Nafion-coated thin-film palladium electrodes Erikson, Heiki; Kasikov, Aarne; Johans, Christoffer Journal of Electroanalytical Chemistry, Vol. 652, Issue 1-2 https://doi.org/10.1016/j.jelechem.2010.12.021	journal	March 2011
Recent progress in oxygen reduction electrocatalysis on Pd-based catalysts Erikson, Heiki; Sarapuu, Ave; Solla-Gullón, Jose Journal of Electroanalytical Chemistry, Vol. 780 https://doi.org/10.1016/j.jelechem.2016.09.034	journal	November 2016
Using Microenvironments to Control Reactivity in CO2 Electrocatalysis Hahn, Christopher; Jaramillo, Thomas F. Joule, Vol. 4, Issue 2 https://doi.org/10.1016/j.joule.2020.01.017	journal	February 2020
Synthesis of high dispersed intermetallic Ag4Sn/C and its enhanced oxygen reduction reaction activity Lu, Yuanjun; Zhang, Nanlin; An, Li Journal of Power Sources, Vol. 240 https://doi.org/10.1016/j.jpowsour.2013.05.015	journal	October 2013
Review of cell performance in anion exchange membrane fuel cells Dekel, Dario R. Journal of Power Sources, Vol. 375 https://doi.org/10.1016/j.jpowsour.2017.07.117	journal	January 2018
Bottom-Up Fabrication of Oxygen Reduction Electrodes with Atomic Layer Deposition for High-Power-Density PEMFCs Dull, Samuel M.; Xu, Shicheng; Goh, Timothy Cell Reports Physical Science, Vol. 2, Issue 1 https://doi.org/10.1016/j.xcrp.2020.100297	journal	January 2021
Electrochemical Stripping to Recover Nitrogen from Source-Separated Urine Tarpeh, William A.; Barazesh, James M.; Cath, Tzahi Y. Environmental Science & Technology, Vol. 52, Issue 3 https://doi.org/10.1021/acs.est.7b05488	journal	January 2018
Electric Field Effects in Oxygen Reduction Kinetics: Rationalizing pH Dependence at the Pt(111), Au(111), and Au(100) Electrodes Kelly, Sara R.; Kirk, Charlotte; Chan, Karen The Journal of Physical Chemistry C, Vol. 124, Issue 27 https://doi.org/10.1021/acs.jpcc.0c02127	journal	June 2020
Enhanced Oxygen Reduction Activity by Selective Anion Adsorption on Non-Precious-Metal Catalysts Holst-Olesen, Kaspar; Reda, Mateusz; Hansen, Heine A. ACS Catalysis, Vol. 8, Issue 8 https://doi.org/10.1021/acscatal.8b01584	journal	June 2018
Analysis of Acid-Stable and Active Oxides for the Oxygen Evolution Reaction Gunasooriya, G. T. Kasun Kalhara; Nørskov, Jens K. ACS Energy Letters, Vol. 5, Issue 12 https://doi.org/10.1021/acsenergylett.0c02030	journal	November 2020
Oxygen Electroreduction at High-Index Pt Electrodes in Alkaline Electrolytes: A Decisive Role of the Alkali Metal Cations Garlyyev, Batyr; Xue, Song; Pohl, Marcus D. ACS Omega, Vol. 3, Issue 11 https://doi.org/10.1021/acsomega.8b00298	journal	November 2018
Electrolyte Engineering for Efficient Electrochemical Nitrate Reduction to Ammonia on a Titanium Electrode McEnaney, Joshua M.; Blair, Sarah J.; Nielander, Adam C. ACS Sustainable Chemistry & Engineering, Vol. 8, Issue 7 https://doi.org/10.1021/acssuschemeng.9b05983	journal	February 2020
Ordered Anion Adlayers on Metal Electrode Surfaces Magnussen, O. M. Chemical Reviews, Vol. 102, Issue 3 https://doi.org/10.1021/cr000069p	journal	March 2002
Synthesis of Pd−Pt Bimetallic Nanocrystals with a Concave Structure through a Bromide-Induced Galvanic Replacement Reaction Zhang, Hui; Jin, Mingshang; Wang, Jinguo Journal of the American Chemical Society, Vol. 133, Issue 15 https://doi.org/10.1021/ja201156s	journal	April 2011
Promoter Effects of Alkali Metal Cations on the Electrochemical Reduction of Carbon Dioxide Resasco, Joaquin; Chen, Leanne D.; Clark, Ezra Journal of the American Chemical Society, Vol. 139, Issue 32 https://doi.org/10.1021/jacs.7b06765	journal	August 2017
Suppressing Ion Transfer Enables Versatile Measurements of Electrochemical Surface Area for Intrinsic Activity Comparisons Yoon, Youngmin; Yan, Bing; Surendranath, Yogesh Journal of the American Chemical Society, Vol. 140, Issue 7 https://doi.org/10.1021/jacs.7b10966	journal	February 2018
Anion Adsorption, CO Oxidation, and Oxygen Reduction Reaction on a Au(100) Surface: The pH Effect Blizanac, B. B.; Lucas, C. A.; Gallagher, M. E. The Journal of Physical Chemistry B, Vol. 108, Issue 2 https://doi.org/10.1021/jp036483l	journal	January 2004
Kinetic Analysis of Oxygen Reduction on Pt(111) in Acid Solutions: Intrinsic Kinetic Parameters and Anion Adsorption Effects Wang, J. X.; Markovic, N. M.; Adzic, R. R. The Journal of Physical Chemistry B, Vol. 108, Issue 13, p. 4127-4133 https://doi.org/10.1021/jp037593v	journal	April 2004
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
Oxygen Reduction on Silver Low-Index Single-Crystal Surfaces in Alkaline Solution: Rotating Ring Disk_Ag(hkl) Studies Blizanac, B. B.; Ross, P. N.; Marković, N. M. The Journal of Physical Chemistry B, Vol. 110, Issue 10, p. 4735-4741 https://doi.org/10.1021/jp056050d	journal	March 2006
Active Sites for the Oxygen Reduction Reaction on the Low and High Index Planes of Palladium Kondo, Shinpei; Nakamura, Masashi; Maki, Norihito The Journal of Physical Chemistry C, Vol. 113, Issue 29 https://doi.org/10.1021/jp904278b	journal	June 2009
Effects of Li ⁺ , K ⁺ , and Ba ²⁺ Cations on the ORR at Model and High Surface Area Pt and Au Surfaces in Alkaline Solutions Strmcnik, D.; van der Vliet, D. F.; Chang, K. -C. The Journal of Physical Chemistry Letters, Vol. 2, Issue 21 https://doi.org/10.1021/jz201215u	journal	October 2011
Electrosorption Valency and Partial Charge Transfer in Halide and Sulfide Adsorption on Ag(111) Foresti, Maria Luisa; Innocenti, Massimo; Forni, Francesca Langmuir, Vol. 14, Issue 24 https://doi.org/10.1021/la980692t	journal	November 1998
High-performance Ag–Co alloy catalysts for electrochemical oxygen reduction Holewinski, Adam; Idrobo, Juan-Carlos; Linic, Suljo Nature Chemistry, Vol. 6, Issue 9 https://doi.org/10.1038/nchem.2032	journal	August 2014
Effect of hydrophobic cations on the oxygen reduction reaction on single‒crystal platinum electrodes Kumeda, Tomoaki; Tajiri, Hiroo; Sakata, Osami Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-06917-4	journal	November 2018
Tuning the electronic structure of Ag-Pd alloys to enhance performance for alkaline oxygen reduction Zamora Zeledón, José A.; Stevens, Michaela Burke; Gunasooriya, G. T. Kasun Kalhara Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-20923-z	journal	January 2021
The role of surface oxygenated-species and adsorbed hydrogen in the oxygen reduction reaction (ORR) mechanism and product selectivity on Pd-based catalysts in acid media Rahul, R.; Singh, R. K.; Bera, B. Physical Chemistry Chemical Physics, Vol. 17, Issue 23 https://doi.org/10.1039/C5CP00692A	journal	January 2015
Ni–Pd core–shell nanoparticles with Pt-like oxygen reduction electrocatalytic performance in both acidic and alkaline electrolytes Jiang, Jun; Gao, Han; Lu, Shu Journal of Materials Chemistry A, Vol. 5, Issue 19 https://doi.org/10.1039/C7TA01754E	journal	January 2017
Electrocatalysis of oxygen reduction on heteroatom-doped nanocarbons and transition metal–nitrogen–carbon catalysts for alkaline membrane fuel cells Sarapuu, Ave; Kibena-Põldsepp, Elo; Borghei, Maryam Journal of Materials Chemistry A, Vol. 6, Issue 3 https://doi.org/10.1039/C7TA08690C	journal	January 2018
The role of anions in surface electrochemistry Tripkovic, D. V.; Strmcnik, D.; van der Vliet, D. Faraday Discuss., Vol. 140 https://doi.org/10.1039/b803714k	journal	January 2009
Surface Pourbaix diagrams and oxygen reduction activity of Pt, Ag and Ni(111) surfaces studied by DFT Hansen, Heine A.; Rossmeisl, Jan; Nørskov, Jens K. Physical Chemistry Chemical Physics, Vol. 10, Issue 25 https://doi.org/10.1039/b803956a	journal	January 2008
Catalysis at the nanoscale may change selectivity Costentin, Cyrille; Savéant, Jean-Michel Proceedings of the National Academy of Sciences, Vol. 113, Issue 42 https://doi.org/10.1073/pnas.1613406113	journal	September 2016
The atomic simulation environment—a Python library for working with atoms Hjorth Larsen, Ask; Jørgen Mortensen, Jens; Blomqvist, Jakob Journal of Physics: Condensed Matter, Vol. 29, Issue 27 https://doi.org/10.1088/1361-648X/aa680e	journal	June 2017
Special points for Brillouin-zone integrations Monkhorst, Hendrik J.; Pack, James D. Physical Review B, Vol. 13, Issue 12, p. 5188-5192 https://doi.org/10.1103/PhysRevB.13.5188	journal	June 1976
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
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals Hammer, B.; Hansen, L. B.; Nørskov, J. K. Physical Review B, Vol. 59, Issue 11 https://doi.org/10.1103/PhysRevB.59.7413	journal	March 1999
Palladium Electrode in Oxygen‐Saturated Aqueous Solutions: Potential Dependent Adsorption of Oxygen Containing Species and Their Effect on Oxygen Reduction Vracar, Lj. M.; Sepa, D. B.; Damjanovic, A. Journal of The Electrochemical Society, Vol. 136, Issue 7 https://doi.org/10.1149/1.2097105	journal	July 1989
The Catalytic Activity of Platinum Supported on Carbon for Electrochemical Oxygen Reduction in Phosphoric Acid Kunz, H. R.; Gruver, G. A. Journal of The Electrochemical Society, Vol. 122, Issue 10 https://doi.org/10.1149/1.2134000	journal	October 1975
Fundamental Mechanistic Understanding of Electrocatalysis of Oxygen Reduction on Pt and Non-Pt Surfaces: Acid versus Alkaline Media Ramaswamy, Nagappan; Mukerjee, Sanjeev Advances in Physical Chemistry, Vol. 2012 https://doi.org/10.1155/2012/491604	journal	March 2012
CRC Handbook of Chemistry and Physics Haynes, W. M.; Lide, David R.; Bruno, Thomas J. CRC press https://doi.org/10.1201/9781315380476	book	June 2016
Gwyddion: an open-source software for SPM data analysis Nečas, David; Klapetek, Petr Open Physics, Vol. 10, Issue 1 https://doi.org/10.2478/s11534-011-0096-2	journal	January 2012
Sulfate, Bisulfate, and Hydrogen Co-adsorption on Pt(111) and Au(111) in an Electrochemical Environment Gossenberger, Florian; Juarez, Fernanda; Groß, Axel Frontiers in Chemistry, Vol. 8 https://doi.org/10.3389/fchem.2020.00634	journal	July 2020

Similar Records

Acid anion electrolyte effects on platinum for oxygen and hydrogen electrocatalysis

Journal Article · Thu Feb 17 19:00:00 EST 2022 · Communications Chemistry · OSTI ID:1841467

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
acid
anions
interfaces
microenvironment
oxygen reduction

Probing the Effects of Acid Electrolyte Anions on Electrocatalyst Activity and Selectivity for the Oxygen Reduction Reaction

Citation Formats

References (72)

Similar Records

Related Subjects