Acid–Base Chemistry of a Model IrO2 Catalytic Interface

Raman, Abhinav S.; Selloni, Annabella

doi:10.1021/acs.jpclett.3c02001

Title: Acid–Base Chemistry of a Model IrO₂ Catalytic Interface

Journal Article · 23 August 2023 · Journal of Physical Chemistry Letters

DOI: https://doi.org/10.1021/acs.jpclett.3c02001 · OSTI ID:2203078

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Princeton University, NJ (United States); Princeton University
Princeton University, NJ (United States)

Iridium oxide (IrO₂) is one of the most efficient catalytic materials for the oxygen evolution reaction (OER), yet the atomic scale structure of its aqueous interface is largely unknown. Herein, the hydration structure, proton transfer mechanisms and acid-base properties of the rutile IrO₂(110)-water interface are investigated using ab-initio based deep neural-network potentials and enhanced sampling simulations. The proton affinities of the different surface sites are characterized by calculating their acid dissociation constants, which yield a point of zero-charge in good agreement with experiments. A large fraction (≈ 80%) of adsorbed water dissociation is observed, together with a short lifetime (≈ 0.5 ns) of the resulting terminal hydroxy groups, due to rapid proton exchanges between adsorbed H₂O and adjacent OH species. As a result, this rapid surface proton transfer supports the suggestion that the rate-determining step in the OER may not involve proton transfer across the double layer into solution, as indicated by recent experiments.

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Research Organization:: Princeton University, NJ (United States)

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

Grant/Contract Number:: AC02-05CH11231; SC0007347; SC0019394

OSTI ID:: 2203078

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 35 Vol. 14; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (53)

The Common Intermediates of Oxygen Evolution and Dissolution Reactions during Water Electrolysis on Iridium Kasian, Olga; Grote, Jan-Philipp; Geiger, Simon Angewandte Chemie International Edition, Vol. 57, Issue 9 https://doi.org/10.1002/anie.201709652	journal	February 2018
Probing the Mineral–Water Interface with Nonlinear Optical Spectroscopy Backus, Ellen H. G.; Schaefer, Jan; Bonn, Mischa Angewandte Chemie International Edition, Vol. 60, Issue 19 https://doi.org/10.1002/anie.202003085	journal	December 2020
Inter‐relationships between Oxygen Evolution and Iridium Dissolution Mechanisms Lončar, Anja; Escalera‐López, Daniel; Cherevko, Serhiy Angewandte Chemie International Edition, Vol. 61, Issue 14 https://doi.org/10.1002/anie.202114437	journal	February 2022
Universality in Oxygen Evolution Electrocatalysis on Oxide Surfaces Man, Isabela C.; Su, Hai‐Yan; Calle‐Vallejo, Federico ChemCatChem, Vol. 3, Issue 7 https://doi.org/10.1002/cctc.201000397	journal	March 2011
Metal Oxides in Heterogeneous Oxidation Catalysis: State of the Art and Challenges for a More Sustainable World Védrine, Jacques C. ChemSusChem, Vol. 12, Issue 3 https://doi.org/10.1002/cssc.201802248	journal	January 2019
Investigations of water/oxide interfaces by molecular dynamics simulations Wang, Ruiyu; Klein, Michael L.; Carnevale, Vincenzo WIREs Computational Molecular Science, Vol. 11, Issue 6 https://doi.org/10.1002/wcms.1537	journal	June 2021
Oxygen and hydrogen evolution reactions on Ru, RuO 2 , Ir, and IrO 2 thin film electrodes in acidic and alkaline electrolytes: A comparative study on activity and stability Cherevko, Serhiy; Geiger, Simon; Kasian, Olga Catalysis Today, Vol. 262 https://doi.org/10.1016/j.cattod.2015.08.014	journal	March 2016
pH dependence of OER activity of oxides: Current and future perspectives Giordano, Livia; Han, Binghong; Risch, Marcel Catalysis Today, Vol. 262 https://doi.org/10.1016/j.cattod.2015.10.006	journal	March 2016
Isoelectric points and points of zero charge of metal (hydr)oxides: 50years after Parks' review Kosmulski, Marek Advances in Colloid and Interface Science, Vol. 238 https://doi.org/10.1016/j.cis.2016.10.005	journal	December 2016
Stability and dissolution of electrocatalysts: Building the bridge between model and “real world” systems Cherevko, Serhiy Current Opinion in Electrochemistry, Vol. 8 https://doi.org/10.1016/j.coelec.2018.03.034	journal	March 2018
Rationality in the new oxygen evolution catalyst development Pittkowski, Rebecca; Krtil, Petr; Rossmeisl, Jan Current Opinion in Electrochemistry, Vol. 12 https://doi.org/10.1016/j.coelec.2018.11.014	journal	December 2018
Stability of nanostructured iridium oxide electrocatalysts during oxygen evolution reaction in acidic environment Cherevko, Serhiy; Reier, Tobias; Zeradjanin, Aleksandar R. Electrochemistry Communications, Vol. 48 https://doi.org/10.1016/j.elecom.2014.08.027	journal	November 2014
Stability challenges of electrocatalytic oxygen evolution reaction: From mechanistic understanding to reactor design Chen, Feng-Yang; Wu, Zhen-Yu; Adler, Zachary Joule, Vol. 5, Issue 7 https://doi.org/10.1016/j.joule.2021.05.005	journal	July 2021
Importance of Water Structure and Catalyst–Electrolyte Interface on the Design of Water Splitting Catalysts Zhang, Ronguang; Pearce, Paul E.; Duan, Yan Chemistry of Materials, Vol. 31, Issue 20 https://doi.org/10.1021/acs.chemmater.9b02318	journal	August 2019
Computing Surface Acidity Constants of Proton Hopping Groups from Density Functional Theory-Based Molecular Dynamics: Application to the SnO ₂ (110)/H ₂ O Interface Jia, Mei; Zhang, Chao; Cox, Stephen J. Journal of Chemical Theory and Computation, Vol. 16, Issue 10 https://doi.org/10.1021/acs.jctc.0c00021	journal	August 2020
Importance of Surface IrO _x in Stabilizing RuO ₂ for Oxygen Evolution Escudero-Escribano, María; Pedersen, Anders F.; Paoli, Elisa A. The Journal of Physical Chemistry B, Vol. 122, Issue 2 https://doi.org/10.1021/acs.jpcb.7b07047	journal	November 2017
Providing Atomistic Insights into the Dissolution of Rutile Oxides in Electrocatalytic Water Splitting Raman, Abhinav S.; Vojvodic, Aleksandra The Journal of Physical Chemistry C, Vol. 126, Issue 2 https://doi.org/10.1021/acs.jpcc.1c08737	journal	January 2022
pH Dependence of MgO, TiO₂, and γ-Al₂O₃ Surface Chemistry from First Principles Di Liberto, Giovanni; Maleki, Farahnaz; Pacchioni, Gianfranco The Journal of Physical Chemistry C, Vol. 126, Issue 24 https://doi.org/10.1021/acs.jpcc.2c02289	journal	June 2022
Solvation Effects for Oxygen Evolution Reaction Catalysis on IrO ₂ (110) Gauthier, Joseph A.; Dickens, Colin F.; Chen, Leanne D. The Journal of Physical Chemistry C, Vol. 121, Issue 21 https://doi.org/10.1021/acs.jpcc.7b02383	journal	May 2017
Ab Initio Thermodynamics of Iridium Surface Oxidation and Oxygen Evolution Reaction Klyukin, Konstantin; Zagalskaya, Alexandra; Alexandrov, Vitaly The Journal of Physical Chemistry C, Vol. 122, Issue 51 https://doi.org/10.1021/acs.jpcc.8b09868	journal	November 2018
Mechanistic Study of IrO ₂ Dissolution during the Electrocatalytic Oxygen Evolution Reaction Zagalskaya, Alexandra; Alexandrov, Vitaly The Journal of Physical Chemistry Letters, Vol. 11, Issue 7 https://doi.org/10.1021/acs.jpclett.0c00335	journal	March 2020
pH-Dependent Surface Chemistry from First Principles: Application to the BiVO ₄ (010)–Water Interface Ambrosio, Francesco; Wiktor, Julia; Pasquarello, Alfredo ACS Applied Materials & Interfaces, Vol. 10, Issue 12 https://doi.org/10.1021/acsami.7b16545	journal	March 2018
Nanoporous Iridium-Based Alloy Nanowires as Highly Efficient Electrocatalysts Toward Acidic Oxygen Evolution Reaction Wang, Ying; Zhang, Lei; Yin, Kuibo ACS Applied Materials & Interfaces, Vol. 11, Issue 43 https://doi.org/10.1021/acsami.9b09412	journal	October 2019
Fundamental Studies of Planar Single-Crystalline Oxide Model Electrodes (RuO ₂ , IrO ₂ ) for Acidic Water Splitting Over, Herbert ACS Catalysis, Vol. 11, Issue 14 https://doi.org/10.1021/acscatal.1c01973	journal	July 2021
Operando Structure–Activity–Stability Relationship of Iridium Oxides during the Oxygen Evolution Reaction Mom, Rik V.; Falling, Lorenz J.; Kasian, Olga ACS Catalysis, Vol. 12, Issue 9 https://doi.org/10.1021/acscatal.1c05951	journal	April 2022
Iridium-Based Nanowires as Highly Active, Oxygen Evolution Reaction Electrocatalysts Alia, Shaun M.; Shulda, Sarah; Ngo, Chilan ACS Catalysis, Vol. 8, Issue 3 https://doi.org/10.1021/acscatal.7b03787	journal	January 2018
Self-Supported Hydrous Iridium–Nickel Oxide Two-Dimensional Nanoframes for High Activity Oxygen Evolution Electrocatalysts Godínez-Salomón, Fernando; Albiter, Luis; Alia, Shaun M. ACS Catalysis, Vol. 8, Issue 11 https://doi.org/10.1021/acscatal.8b02171	journal	September 2018
Ab Initio Thermodynamics Insight into the Structural Evolution of Working IrO ₂ Catalysts in Proton-Exchange Membrane Electrolyzers Opalka, Daniel; Scheurer, Christoph; Reuter, Karsten ACS Catalysis, Vol. 9, Issue 6 https://doi.org/10.1021/acscatal.9b00796	journal	April 2019
Role of Defects in the Interplay between Adsorbate Evolving and Lattice Oxygen Mechanisms of the Oxygen Evolution Reaction in RuO ₂ and IrO ₂ Zagalskaya, Alexandra; Alexandrov, Vitaly ACS Catalysis, Vol. 10, Issue 6 https://doi.org/10.1021/acscatal.9b05544	journal	February 2020
Rational Design of Rhodium–Iridium Alloy Nanoparticles as Highly Active Catalysts for Acidic Oxygen Evolution Guo, Hongyu; Fang, Zhiwei; Li, Hao ACS Nano, Vol. 13, Issue 11 https://doi.org/10.1021/acsnano.9b06244	journal	October 2019
Redox Potentials and Acidity Constants from Density Functional Theory Based Molecular Dynamics Cheng, Jun; Liu, Xiandong; VandeVondele, Joost Accounts of Chemical Research, Vol. 47, Issue 12 https://doi.org/10.1021/ar500268y	journal	October 2014
Acidity of the Aqueous Rutile TiO ₂ (110) Surface from Density Functional Theory Based Molecular Dynamics Cheng, Jun; Sprik, Michiel Journal of Chemical Theory and Computation, Vol. 6, Issue 3 https://doi.org/10.1021/ct100013q	journal	February 2010
Increasing Iridium Oxide Activity for the Oxygen Evolution Reaction with Hafnium Modification Zhao, Fang; Wen, Bo; Niu, Wenhan Journal of the American Chemical Society, Vol. 143, Issue 38 https://doi.org/10.1021/jacs.1c03473	journal	September 2021
The Reaction Mechanism with Free Energy Barriers at Constant Potentials for the Oxygen Evolution Reaction at the IrO ₂ (110) Surface Ping, Yuan; Nielsen, Robert J.; Goddard, William A. Journal of the American Chemical Society, Vol. 139, Issue 1 https://doi.org/10.1021/jacs.6b07557	journal	December 2016
Influence of Surface Adsorption on the Oxygen Evolution Reaction on IrO ₂ (110) Kuo, Ding-Yuan; Kawasaki, Jason K.; Nelson, Jocienne N. Journal of the American Chemical Society, Vol. 139, Issue 9 https://doi.org/10.1021/jacs.6b11932	journal	February 2017
Influence of Adsorbed Water on the Oxygen Evolution Reaction on Oxides Siahrostami, S.; Vojvodic, A. The Journal of Physical Chemistry C, Vol. 119, Issue 2 https://doi.org/10.1021/jp508932x	journal	December 2014
Balancing activity, stability and conductivity of nanoporous core-shell iridium/iridium oxide oxygen evolution catalysts Kim, Yong-Tae; Lopes, Pietro Papa; Park, Shin-Ae Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-01734-7	journal	November 2017
On the limitations in assessing stability of oxygen evolution catalysts using aqueous model electrochemical cells Knöppel, Julius; Möckl, Maximilian; Escalera-López, Daniel Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-22296-9	journal	April 2021
Confinement effects and acid strength in zeolites Grifoni, Emanuele; Piccini, GiovanniMaria; Lercher, Johannes A. Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-22936-0	journal	May 2021
Introducing Brønsted acid sites to accelerate the bridging-oxygen-assisted deprotonation in acidic water oxidation Wen, Yunzhou; Liu, Cheng; Huang, Rui Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-32581-w	journal	August 2022
Molecular-scale mechanisms of CO2 mineralization in nanoscale interfacial water films Abdolhosseini Qomi, M. J.; Miller, Q. R. S.; Zare, S. Nature Reviews Chemistry, Vol. 6, Issue 9 https://doi.org/10.1038/s41570-022-00418-1	journal	August 2022
Theoretical insights into the surface physics and chemistry of redox-active oxides Rousseau, Roger; Glezakou, Vassiliki-Alexandra; Selloni, Annabella Nature Reviews Materials, Vol. 5, Issue 6 https://doi.org/10.1038/s41578-020-0198-9	journal	May 2020
Key role of chemistry versus bias in electrocatalytic oxygen evolution Nong, Hong Nhan; Falling, Lorenz J.; Bergmann, Arno Nature, Vol. 587, Issue 7834 https://doi.org/10.1038/s41586-020-2908-2	journal	November 2020
Heterogeneous electrocatalysis goes chemical Boettcher, Shannon W.; Surendranath, Yogesh Nature Catalysis, Vol. 4, Issue 1 https://doi.org/10.1038/s41929-020-00570-1	journal	January 2021
Free energy of proton transfer at the water–TiO ₂ interface from ab initio deep potential molecular dynamics Calegari Andrade, Marcos F.; Ko, Hsin-Yu; Zhang, Linfeng Chemical Science, Vol. 11, Issue 9 https://doi.org/10.1039/C9SC05116C	journal	January 2020
A deep potential model with long-range electrostatic interactions Zhang, Linfeng; Wang, Han; Muniz, Maria Carolina The Journal of Chemical Physics, Vol. 156, Issue 12 https://doi.org/10.1063/5.0083669	journal	March 2022
Microscopic description of acid–base equilibrium Grifoni, Emanuele; Piccini, GiovanniMaria; Parrinello, Michele Proceedings of the National Academy of Sciences, Vol. 116, Issue 10 https://doi.org/10.1073/pnas.1819771116	journal	February 2019
Machine learning potentials for complex aqueous systems made simple Schran, Christoph; Thiemann, Fabian L.; Rowe, Patrick Proceedings of the National Academy of Sciences, Vol. 118, Issue 38 https://doi.org/10.1073/pnas.2110077118	journal	September 2021
Water dissociation at the water–rutile TiO ₂ (110) interface from ab initio-based deep neural network simulations Wen, Bo; Calegari Andrade, Marcos F.; Liu, Li-Min Proceedings of the National Academy of Sciences, Vol. 120, Issue 2 https://doi.org/10.1073/pnas.2212250120	journal	January 2023
Strongly Constrained and Appropriately Normed Semilocal Density Functional Sun, Jianwei; Ruzsinszky, Adrienn; Perdew, John P. Physical Review Letters, Vol. 115, Issue 3 https://doi.org/10.1103/PhysRevLett.115.036402	journal	July 2015
Deep Potential Molecular Dynamics: A Scalable Model with the Accuracy of Quantum Mechanics Zhang, Linfeng; Han, Jiequn; Wang, Han Physical Review Letters, Vol. 120, Issue 14 https://doi.org/10.1103/PhysRevLett.120.143001	journal	April 2018
Active learning of uniformly accurate interatomic potentials for materials simulation Zhang, Linfeng; Lin, De-Ye; Wang, Han Physical Review Materials, Vol. 3, Issue 2 https://doi.org/10.1103/PhysRevMaterials.3.023804	journal	February 2019
Combining theory and experiment in electrocatalysis: Insights into materials design Seh, Zhi Wei; Kibsgaard, Jakob; Dickens, Colin F. Science, Vol. 355, Issue 6321 https://doi.org/10.1126/science.aad4998	journal	January 2017

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