Modifying Interface Solvation and Oxygen Reduction Electrocatalysis with Hydrophobic Species

Gawas, Ramchandra; Snyder, Joshua; Tang, Maureen

doi:10.1021/acs.jpcc.2c05169

Modifying Interface Solvation and Oxygen Reduction Electrocatalysis with Hydrophobic Species

Journal Article · Fri Aug 19 04:00:00 EDT 2022 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.2c05169· OSTI ID:2228286

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Drexel University, Philadelphia, PA (United States); Drexel University
Drexel University, Philadelphia, PA (United States)

Ionic liquid interlayers improve the oxygen reduction reaction (ORR) kinetics on bulk and nanostructured catalysts for both Pt and alloyed-Pt materials. Despite the demonstrated performance enhancement at the half-cell and membrane electrode assembly level, the mechanism of the improvement is not fully understood. In this work, we combine single-crystal experiments with microkinetic modeling to uncover the origin of the ORR kinetic improvement on Pt(111) in the presence of ionic liquids and hydrophobic cations. With the incorporation of a modified Frumkin isotherm, our model accurately simulates the disorder–order transition observed in hydroxyl and bisulfate adsorption on Pt(111) under acidic conditions. Voltametric analysis shows that ionic liquids impact solvation to break so-called scaling relations between the adsorption strength of OH_ad and O_ad, but these effects have little impact on ORR activity. Instead, destabilized OH_ad reduces the overall hydroxyl (spectator) coverage, resulting in higher availability of active sites.

View Accepted Manuscript (DOE)

Research Organization:: Drexel University, Philadelphia, PA (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Hydrogen Fuel Cell Technologies Office (HFTO)

Grant/Contract Number:: EE0008434

OSTI ID:: 2228286

Alternate ID(s):: OSTI ID: 1978079

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 34 Vol. 126; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (54)

Oxygen Reduction Reaction on Pt and Pt Bimetallic Surfaces: A Selective Review Marković, N. M.; Schmidt, T. J.; Stamenković, V. Fuel Cells, Vol. 1, Issue 2 https://doi.org/10.1002/1615-6854(200107)1:2<105::AID-FUCE105>3.0.CO;2-9	journal	July 2001
Oxygen Reduction Reaction Performance of [MTBD][beti]-Encapsulated Nanoporous NiPt Alloy Nanoparticles Snyder, Joshua; Livi, Kenneth; Erlebacher, Jonah Advanced Functional Materials, Vol. 23, Issue 44 https://doi.org/10.1002/adfm.201301144	journal	June 2013
Tuning Nanoparticle Catalysis for the Oxygen Reduction Reaction Guo, Shaojun; Zhang, Sen; Sun, Shouheng Angewandte Chemie International Edition, Vol. 52, Issue 33 https://doi.org/10.1002/anie.201207186	journal	June 2013
Accelerating Oxygen-Reduction Catalysts through Preventing Poisoning with Non-Reactive Species by Using Hydrophobic Ionic Liquids Zhang, Gui-Rong; Munoz, Macarena; Etzold, Bastian J. M. Angewandte Chemie International Edition, Vol. 55, Issue 6 https://doi.org/10.1002/anie.201508338	journal	December 2015
Unifying Solution and Surface Electrochemistry: Limitations and Opportunities in Surface Electrocatalysis Viswanathan, Venkatasubramanian; Hansen, Heine Anton Topics in Catalysis, Vol. 57, Issue 1-4 https://doi.org/10.1007/s11244-013-0171-6	journal	October 2013
Pt-based alloy/carbon black nanohybrid covered with ionic liquid supramolecules as an efficient catalyst for oxygen reduction reactions Tran, Quoc Chinh; Dao, Van-Duong; Kim, Hyun You Applied Catalysis B: Environmental, Vol. 204 https://doi.org/10.1016/j.apcatb.2016.11.051	journal	May 2017
Solvation effects on DFT predictions of ORR activity on metal surfaces Zhang, Qiang; Asthagiri, Aravind Catalysis Today, Vol. 323 https://doi.org/10.1016/j.cattod.2018.07.036	journal	February 2019
Thermodynamic analysis of (bi)sulphate adsorption on a Pt(111) electrode as a function of pH Garcia-Araez, Nuria; Climent, Victor; Rodriguez, Paramaconi Electrochimica Acta, Vol. 53, Issue 23 https://doi.org/10.1016/j.electacta.2007.12.086	journal	October 2008
The oxygen reduction reaction mechanism on Pt(111) from density functional theory calculations Tripković, Vladimir; Skúlason, Egill; Siahrostami, Samira Electrochimica Acta, Vol. 55, Issue 27 https://doi.org/10.1016/j.electacta.2010.02.056	journal	November 2010
Towards the understanding of the interfacial pH scale at Pt(1 1 1) electrodes Rizo, Rubén; Sitta, Elton; Herrero, Enrique Electrochimica Acta, Vol. 162 https://doi.org/10.1016/j.electacta.2015.01.069	journal	April 2015
Ionic liquids in electrocatalysis Zhang, Gui-Rong; Etzold, Bastian J. M. Journal of Energy Chemistry, Vol. 25, Issue 2 https://doi.org/10.1016/j.jechem.2016.01.007	journal	March 2016
Partial and complete reduction of O2 by hydrogen on transition metal surfaces Ford, Denise C.; Nilekar, Anand Udaykumar; Xu, Ye Surface Science, Vol. 604, Issue 19-20 https://doi.org/10.1016/j.susc.2010.05.026	journal	September 2010
Recent Advances in Electrocatalysts for Oxygen Reduction Reaction Shao, Minhua; Chang, Qiaowan; Dodelet, Jean-Pol Chemical Reviews, Vol. 116, Issue 6 https://doi.org/10.1021/acs.chemrev.5b00462	journal	February 2016
Understanding Catalytic Activity Trends in the Oxygen Reduction Reaction Kulkarni, Ambarish; Siahrostami, Samira; Patel, Anjli Chemical Reviews, Vol. 118, Issue 5 https://doi.org/10.1021/acs.chemrev.7b00488	journal	December 2017
Combining Single Crystal Experiments and Microkinetic Modeling in Disentangling Thermodynamic, Kinetic, and Double-Layer Factors Influencing Oxygen Reduction Zhou, Da; Wei, Jie; He, Zheng-Da The Journal of Physical Chemistry C, Vol. 124, Issue 25 https://doi.org/10.1021/acs.jpcc.0c01621	journal	May 2020
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
Importance of Solvation for the Accurate Prediction of Oxygen Reduction Activities of Pt-Based Electrocatalysts He, Zheng-Da; Hanselman, Selwyn; Chen, Yan-Xia The Journal of Physical Chemistry Letters, Vol. 8, Issue 10 https://doi.org/10.1021/acs.jpclett.7b01018	journal	May 2017
First-Principles Calculation of Pt Surface Energies in an Electrochemical Environment: Thermodynamic Driving Forces for Surface Faceting and Nanoparticle Reconstruction McCrum, Ian T.; Hickner, Michael A.; Janik, Michael J. Langmuir, Vol. 33, Issue 28 https://doi.org/10.1021/acs.langmuir.7b01530	journal	July 2017
Improved Rate for the Oxygen Reduction Reaction in a Sulfuric Acid Electrolyte using a Pt(111) Surface Modified with Melamine Zorko, Milena; Farinazzo Bergamo Dias Martins, Pedro; Connell, Justin G. ACS Applied Materials & Interfaces, Vol. 13, Issue 2 https://doi.org/10.1021/acsami.0c18167	journal	January 2021
Effect of Hydrophobic Cations on the Inhibitors for the Oxygen Reduction Reaction on Anions and Ionomers Adsorbed on Single-Crystal Pt Electrodes Kumeda, Tomoaki; Hoshi, Nagahiro; Nakamura, Masashi ACS Applied Materials & Interfaces, Vol. 13, Issue 13 https://doi.org/10.1021/acsami.1c01421	journal	March 2021
Ionic Liquid Additives for the Mitigation of Nafion Specific Adsorption on Platinum Li, Yawei; Intikhab, Saad; Malkani, Arnav ACS Catalysis, Vol. 10, Issue 14 https://doi.org/10.1021/acscatal.0c01243	journal	June 2020
Adsorbed Hydroxide Does Not Participate in the Volmer Step of Alkaline Hydrogen Electrocatalysis Intikhab, Saad; Snyder, Joshua D.; Tang, Maureen H. ACS Catalysis, Vol. 7, Issue 12 https://doi.org/10.1021/acscatal.7b02787	journal	November 2017
Tuning the Electrocatalytic Performance of Ionic Liquid Modified Pt Catalysts for the Oxygen Reduction Reaction via Cationic Chain Engineering Zhang, Gui-Rong; Wolker, Thomas; Sandbeck, Daniel J. S. ACS Catalysis, Vol. 8, Issue 9 https://doi.org/10.1021/acscatal.8b02018	journal	July 2018
Effect of Ionic Liquid Modification on the ORR Performance and Degradation Mechanism of Trimetallic PtNiMo/C Catalysts George, Michael; Zhang, Gui-Rong; Schmitt, Nicolai ACS Catalysis, Vol. 9, Issue 9 https://doi.org/10.1021/acscatal.9b01772	journal	August 2019
Sequential Capacitive Deposition of Ionic Liquids for Conformal Thin Film Coatings on Oxygen Reduction Reaction Electrocatalysts Li, Yawei; Hart, James; Profitt, Lauren ACS Catalysis, Vol. 9, Issue 10 https://doi.org/10.1021/acscatal.9b03157	journal	September 2019
Modifying the Electrocatalyst–Ionomer Interface via Sulfonated Poly(ionic liquid) Block Copolymers to Enable High-Performance Polymer Electrolyte Fuel Cells Li, Yawei; Van Cleve, Tim; Sun, Rui ACS Energy Letters, Vol. 5, Issue 6 https://doi.org/10.1021/acsenergylett.0c00532	journal	April 2020
Boosting Performance of Low Temperature Fuel Cell Catalysts by Subtle Ionic Liquid Modification Zhang, Gui-Rong; Munoz, Macarena; Etzold, Bastian J. M. ACS Applied Materials & Interfaces, Vol. 7, Issue 6 https://doi.org/10.1021/am5074003	journal	February 2015
Phase Behavior and Crystalline Phases of Ionic Liquid-Lithium Salt Mixtures with 1-Alkyl-3-methylimidazolium Salts ^† Zhou, Qian; Fitzgerald, Kendall; Boyle, Paul D. Chemistry of Materials, Vol. 22, Issue 3 https://doi.org/10.1021/cm902691v	journal	February 2010
Universality in Oxygen Reduction Electrocatalysis on Metal Surfaces Viswanathan, Venkatasubramanian; Hansen, Heine Anton; Rossmeisl, Jan ACS Catalysis, Vol. 2, Issue 8 https://doi.org/10.1021/cs300227s	journal	July 2012
Structure/Processing/Properties Relationships in Nanoporous Nanoparticles As Applied to Catalysis of the Cathodic Oxygen Reduction Reaction Snyder, Joshua; McCue, Ian; Livi, Ken Journal of the American Chemical Society, Vol. 134, Issue 20 https://doi.org/10.1021/ja3019498	journal	May 2012
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
Thermodynamic Analysis of the Temperature Dependence of OH Adsorption on Pt(111) and Pt(100) Electrodes in Acidic Media in the Absence of Specific Anion Adsorption Climent, Víctor; Gómez, Roberto; Orts, José M. The Journal of Physical Chemistry B, Vol. 110, Issue 23 https://doi.org/10.1021/jp054948x	journal	June 2006
Structure and Bonding of the Water−Hydroxyl Mixed Phase on Pt(111) Schiros, T.; Näslund, L. -Å.; Andersson, K. The Journal of Physical Chemistry C, Vol. 111, Issue 41 https://doi.org/10.1021/jp073405f	journal	September 2007
Double-Trap Kinetic Equation for the Oxygen Reduction Reaction on Pt(111) in Acidic Media Wang, Jia X.; Zhang, Junliang; Adzic, Radoslav R. The Journal of Physical Chemistry A, Vol. 111, Issue 49, p. 12702-12710 https://doi.org/10.1021/jp076104e	journal	December 2007
Cooperativity in Surface Bonding and Hydrogen Bonding of Water and Hydroxyl at Metal Surfaces Schiros, T.; Ogasawara, H.; Näslund, L. -Å. The Journal of Physical Chemistry C, Vol. 114, Issue 22 https://doi.org/10.1021/jp101855v	journal	May 2010
Unifying Kinetic and Thermodynamic Analysis of 2 e ^– and 4 e ^– Reduction of Oxygen on Metal Surfaces Hansen, Heine A.; Viswanathan, Venkatasubramanian; Nørskov, Jens K. The Journal of Physical Chemistry C, Vol. 118, Issue 13 https://doi.org/10.1021/jp4100608	journal	March 2014
Superstructures and Order−Disorder Transition of Sulfate Adlayers on Pt(111) in Sulfuric Acid Solution Braunschweig, Björn; Daum, Winfried Langmuir, Vol. 25, Issue 18 https://doi.org/10.1021/la901399j	journal	May 2009
Multimetallic Core/Interlayer/Shell Nanostructures as Advanced Electrocatalysts Kang, Yijin; Snyder, Joshua; Chi, Miaofang Nano Letters, Vol. 14, Issue 11 https://doi.org/10.1021/nl5028205	journal	October 2014
Electrocatalyst approaches and challenges for automotive fuel cells Debe, Mark K. Nature, Vol. 486, Issue 7401 https://doi.org/10.1038/nature11115	journal	June 2012
Direct observation of the oxygenated species during oxygen reduction on a platinum fuel cell cathode Casalongue, Hernan Sanchez; Kaya, Sarp; Viswanathan, Venkatasubramanian Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3817	journal	December 2013
Oxygen reduction in nanoporous metal–ionic liquid composite electrocatalysts Snyder, J.; Fujita, T.; Chen, M. W. Nature Materials, Vol. 9, Issue 11 https://doi.org/10.1038/nmat2878	journal	October 2010
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
Enhancing oxygen reduction electrocatalysis by tuning interfacial hydrogen bonds Wang, Tao; Zhang, Yirui; Huang, Botao Nature Catalysis, Vol. 4, Issue 9 https://doi.org/10.1038/s41929-021-00668-0	journal	September 2021
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
Understanding the electrocatalysis of oxygen reduction on platinum and its alloys Stephens, Ifan E. L.; Bondarenko, Alexander S.; Grønbjerg, Ulrik Energy & Environmental Science, Vol. 5, Issue 5 https://doi.org/10.1039/c2ee03590a	journal	January 2012
Theory of multiple proton–electron transfer reactions and its implications for electrocatalysis Koper, Marc T. M. Chemical Science, Vol. 4, Issue 7 https://doi.org/10.1039/c3sc50205h	journal	January 2013
OH formation and H ₂ adsorption at the liquid water–Pt(111) interface Kristoffersen, Henrik H.; Vegge, Tejs; Hansen, Heine Anton Chemical Science, Vol. 9, Issue 34 https://doi.org/10.1039/c8sc02495b	journal	January 2018
Hydrogen Bonding in Mixed O H + H 2 O Overlayers on Pt(111) Clay, C.; Haq, S.; Hodgson, A. Physical Review Letters, Vol. 92, Issue 4 https://doi.org/10.1103/PhysRevLett.92.046102	journal	January 2004
Improved Oxygen Reduction Activity on Pt₃Ni(111) via Increased Surface Site Availability Stamenkovic, V. R.; Fowler, B.; Mun, B. S. Science, Vol. 315, Issue 5811, p. 493-497 https://doi.org/10.1126/science.1135941	journal	January 2007
Highly Crystalline Multimetallic Nanoframes with Three-Dimensional Electrocatalytic Surfaces Chen, C.; Kang, Y.; Huo, Z. Science, Vol. 343, Issue 6177 https://doi.org/10.1126/science.1249061	journal	February 2014
Characterization of a Sulfonated Poly(Ionic Liquid) Block Copolymer as an Ionomer for Proton Exchange Membrane Fuel Cells using Rotating Disk Electrode Gawas, Ramchandra; Sun, Rui; Li, Yawei Journal of The Electrochemical Society, Vol. 168, Issue 12 https://doi.org/10.1149/1945-7111/ac4375	journal	December 2021
Characterization of Nanoporous Metal-Ionic Liquid Composites for the Electrochemical Oxygen Reduction Reaction Benn, E.; Uvegi, H.; Erlebacher, J. Journal of The Electrochemical Society, Vol. 162, Issue 10 https://doi.org/10.1149/2.0161510jes	journal	January 2015
Enhancing Pt/C Catalysts for the Oxygen Reduction Reaction with Protic Ionic Liquids: The Effect of Anion Structure Huang, Kan; Song, Tangqiumei; Morales-Collazo, Oscar Journal of The Electrochemical Society, Vol. 164, Issue 13 https://doi.org/10.1149/2.1071713jes	journal	January 2017
The Activity Enhancement Effect of Ionic Liquids on Oxygen Reduction Reaction Catalysts: From Rotating Disk Electrode to Membrane Electrode Assembly Huang, Kan; Morales-Collazo, Oscar; Chen, Zhichao Catalysts, Vol. 11, Issue 8 https://doi.org/10.3390/catal11080989	journal	August 2021

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Modifying Interface Solvation and Oxygen Reduction Electrocatalysis with Hydrophobic Species

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References (54)

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