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

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

doi:10.1002/celc.202100500

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

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

^*Corresponding author for this work

Department of Physics

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Abstract

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 pH 1, 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 HNO₃compared 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.

Original language	English
Journal	ChemElectroChem
Volume	8
Issue number	13
Pages (from-to)	2467-2478
ISSN	2196-0216
DOIs	https://doi.org/10.1002/celc.202100500
Publication status	Published - 2021

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Funding Information:
This work was supported by the Toyota Research Institute. Some of the research efforts involving thin film synthesis were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Science Program to the SUNCAT Center for Interface Science and Catalysis. Part of this work was performed at the Stanford Nano Shared Facilities (SNSF), supported by the National Science Foundation under Award ECCS‐2026822. The authors thank Victoria Chen for help in accessing the AFM, Jaime E. Avilés Acosta for performing AFM on a GC substrate, and Melissa E. Kreider for valuable discussions. J.A.Z.Z. gratefully acknowledges support of the Gates Millennium Graduate Fellowship/Scholarship and the Stanford's Office of VPGE EDGE Fellowship. G.A.K. gratefully acknowledges support from the National Science Foundation Graduate Research Fellowship under Grant No. 1650114.

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

abstract = "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 pH 1, 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.",

author = "{Zamora Zeled{\'o}n}, {Jos{\'e} A.} and Kamat, {Gaurav Ashish} and Gunasooriya, {G. T.Kasun Kalhara} and N{\o}rskov, {Jens K.} and Stevens, {Michaela Burke} and Jaramillo, {Thomas F.}",

note = "Funding Information: This work was supported by the Toyota Research Institute. Some of the research efforts involving thin film synthesis were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Science Program to the SUNCAT Center for Interface Science and Catalysis. Part of this work was performed at the Stanford Nano Shared Facilities (SNSF), supported by the National Science Foundation under Award ECCS‐2026822. The authors thank Victoria Chen for help in accessing the AFM, Jaime E. Avil{\'e}s Acosta for performing AFM on a GC substrate, and Melissa E. Kreider for valuable discussions. J.A.Z.Z. gratefully acknowledges support of the Gates Millennium Graduate Fellowship/Scholarship and the Stanford's Office of VPGE EDGE Fellowship. G.A.K. gratefully acknowledges support from the National Science Foundation Graduate Research Fellowship under Grant No. 1650114. ",

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AU - Zamora Zeledón, José A.

AU - Kamat, Gaurav Ashish

AU - Gunasooriya, G. T.Kasun Kalhara

AU - Nørskov, Jens K.

AU - Stevens, Michaela Burke

AU - Jaramillo, Thomas F.

N1 - Funding Information: This work was supported by the Toyota Research Institute. Some of the research efforts involving thin film synthesis were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Science Program to the SUNCAT Center for Interface Science and Catalysis. Part of this work was performed at the Stanford Nano Shared Facilities (SNSF), supported by the National Science Foundation under Award ECCS‐2026822. The authors thank Victoria Chen for help in accessing the AFM, Jaime E. Avilés Acosta for performing AFM on a GC substrate, and Melissa E. Kreider for valuable discussions. J.A.Z.Z. gratefully acknowledges support of the Gates Millennium Graduate Fellowship/Scholarship and the Stanford's Office of VPGE EDGE Fellowship. G.A.K. gratefully acknowledges support from the National Science Foundation Graduate Research Fellowship under Grant No. 1650114.

PY - 2021

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N2 - 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 pH 1, 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.

AB - 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 pH 1, 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.

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DO - 10.1002/celc.202100500

M3 - Journal article

AN - SCOPUS:85110548101

SN - 2196-0216

VL - 8

SP - 2467

EP - 2478

JO - ChemElectroChem

JF - ChemElectroChem

IS - 13

ER -

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

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