ACS Publications. Most Trusted. Most Cited. Most Read
My Activity
CONTENT TYPES

Figure 1Loading Img

Determination of Proton-Coupled Electron Transfer Reorganization Energies with Application to Water Oxidation Catalysts

  • Jenny Schneider
    Jenny Schneider
    Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill 27599, United States
  • Rachel E. Bangle
    Rachel E. Bangle
    Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill 27599, United States
  • Wesley B. Swords
    Wesley B. Swords
    Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill 27599, United States
  • Ludovic Troian-Gautier
    Ludovic Troian-Gautier
    Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill 27599, United States
  • , and 
  • Gerald J. Meyer*
    Gerald J. Meyer
    Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill 27599, United States
    *[email protected]
Cite this: J. Am. Chem. Soc. 2019, 141, 25, 9758–9763
Publication Date (Web):June 3, 2019
https://doi.org/10.1021/jacs.9b01296
Copyright © 2019 American Chemical Society

    Article Views

    3839

    Altmetric

    -

    Citations

    LEARN ABOUT THESE METRICS
    Other access options
    Supporting Info (1)»

    Abstract

    Abstract Image

    The reorganization energy, λ, for interfacial electron transfer (ET) and for proton-coupled electron transfer (PCET) between a water oxidation catalyst and a conductive In2O3:Sn (ITO) oxide were extracted from kinetic data by application of Marcus–Gerischer theory. Specifically, light excitation of the water oxidation catalyst [RuII(tpy)(4,4′-(PO3H2)2-bpy)OH2]2+ (RuII-OH2), where tpy is 2,2′:6′,2″-terpyridine and bpy is 2,2′-bipyridine, anchored to a mesoporous thin film of ITO nanocrystallites resulted in rapid excited-state injection (kinj > 108 s–1). The subsequent reaction of the injected electron (ITO(e)) and the oxidized catalyst was quantified spectroscopically on nanosecond and longer time scales. The metallic character of ITO allowed potentiostatic control of the reaction free energy change −ΔGo over a 1 eV range. At pH values below the pKa = 1.7 of the oxidized catalyst, ET was the primary reaction. Within the pH range 2 ≤ pH ≤ 5, an interfacial PCET reaction (ITO(e) + RuIII-OH + H+→ RuII-OH2) occurred with smaller rate constants. Plots of the rate constants versus −ΔGo provided a reorganization energy of λPCET = 0.9 eV and λET = 0.5 eV. A second water oxidation catalyst provided similar values and demonstrated generality. The utilization of conductive oxides is shown to be a powerful tool for quantifying PCET reorganization energies at oxide surfaces for the first time.

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. You can change your affiliated institution below.

    Supporting Information

    ARTICLE SECTIONS
    Jump To

    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.9b01296.

    • Experimental methods, cyclic voltammograms, kinetic isotope effect, tables with the kinetic data and the corresponding values for the reaction free energy; UV–vis spectrum, plot of E1/2 as a function of pH, kinetic traces, and Marcus–Gerischer analysis of kinetic data obtained with [RuII(tpy)(4,4′-(CH2-PO3H2)2-bpy)OH2]2+ (PDF)

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    This article is cited by 23 publications.

    1. Kai-Yuan Huang, Zhi-Qiang Yang, Ming-Rui Yang, Tian-Shui Chen, Shurong Tang, Wei-Ming Sun, Qiaofeng Yao, Hao-Hua Deng, Wei Chen, Jianping Xie. Unraveling a Concerted Proton-Coupled Electron Transfer Pathway in Atomically Precise Gold Nanoclusters. Journal of the American Chemical Society 2024, 146 (12) , 8706-8715. https://doi.org/10.1021/jacs.4c01180
    2. Matthew C. Kessinger, Jeremiah Xu, Kai Cui, Quentin Loague, Alexander V. Soudackov, Sharon Hammes-Schiffer, Gerald J. Meyer. Direct Evidence for a Sequential Electron Transfer–Proton Transfer Mechanism in the PCET Reduction of a Metal Hydroxide Catalyst. Journal of the American Chemical Society 2024, 146 (3) , 1742-1747. https://doi.org/10.1021/jacs.3c10742
    3. Matthew Kessinger, Alexander V. Soudackov, Jenny Schneider, Rachel E. Bangle, Sharon Hammes-Schiffer, Gerald J. Meyer. Reorganization Energies for Interfacial Proton-Coupled Electron Transfer to a Water Oxidation Catalyst. Journal of the American Chemical Society 2022, 144 (44) , 20514-20524. https://doi.org/10.1021/jacs.2c09672
    4. Marzieh Heidari, Quentin Loague, Rachel E. Bangle, Elena Galoppini, Gerald J. Meyer. Reorganization Energies for Interfacial Electron Transfer across Phenylene Ethynylene Rigid-Rod Bridges. ACS Applied Materials & Interfaces 2022, 14 (30) , 35205-35214. https://doi.org/10.1021/acsami.2c07151
    5. Rishi G. Agarwal, Scott C. Coste, Benjamin D. Groff, Abigail M. Heuer, Hyunho Noh, Giovanny A. Parada, Catherine F. Wise, Eva M. Nichols, Jeffrey J. Warren, James M. Mayer. Free Energies of Proton-Coupled Electron Transfer Reagents and Their Applications. Chemical Reviews 2022, 122 (1) , 1-49. https://doi.org/10.1021/acs.chemrev.1c00521
    6. Md. Hafizur Rahman, Abderrahman Atifi, Joel Rosenthal, Michael D. Ryan. Reversible Proton-Coupled Reduction of an Iron Nitrosyl Porphyrin within [DBU–H]+-Based Protic Ionic Liquid Nanodomains. Inorganic Chemistry 2021, 60 (14) , 10631-10641. https://doi.org/10.1021/acs.inorgchem.1c01273
    7. Ke Hu, Renato N. Sampaio, Jenny Schneider, Ludovic Troian-Gautier, Gerald J. Meyer. Perspectives on Dye Sensitization of Nanocrystalline Mesoporous Thin Films. Journal of the American Chemical Society 2020, 142 (38) , 16099-16116. https://doi.org/10.1021/jacs.0c04886
    8. Rachel E. Bangle, Jenny Schneider, Eric J. Piechota, Ludovic Troian-Gautier, Gerald J. Meyer. Electron Transfer Reorganization Energies in the Electrode–Electrolyte Double Layer. Journal of the American Chemical Society 2020, 142 (2) , 674-679. https://doi.org/10.1021/jacs.9b11815
    9. Austin L. Jones, Kirk S. Schanze. Free Energy Dependence of Photoinduced Electron Transfer in Octathiophene-Diimide Dyads. The Journal of Physical Chemistry A 2020, 124 (1) , 21-29. https://doi.org/10.1021/acs.jpca.9b08622
    10. Rachel E. Bangle, Gerald J. Meyer. Factors that Control the Direction of Excited-State Electron Transfer at Dye-Sensitized Oxide Interfaces. The Journal of Physical Chemistry C 2019, 123 (42) , 25967-25976. https://doi.org/10.1021/acs.jpcc.9b06755
    11. Denis Antipin, Marcel Risch. Calculation of the Tafel slope and reaction order of the oxygen evolution reaction between pH 12 and pH 14 for the adsorbate mechanism. Electrochemical Science Advances 2023, 3 (6) https://doi.org/10.1002/elsa.202100213
    12. Nadav Snir, Maytal Caspary Toroker. Kinetic Properties of Oxygen Evolution Reaction Catalysis in Hematite. Advanced Theory and Simulations 2023, 6 (10) https://doi.org/10.1002/adts.202300182
    13. Xiang‐Zhu Wei, Tian‐Yu Ding, Yang Wang, Bing Yang, Qing‐Qing Yang, Shengfa Ye, Chen‐Ho Tung, Li‐Zhu Wu. Tracking an Fe V (O) Intermediate for Water Oxidation in Water. Angewandte Chemie 2023, 135 (36) https://doi.org/10.1002/ange.202308192
    14. Xiang‐Zhu Wei, Tian‐Yu Ding, Yang Wang, Bing Yang, Qing‐Qing Yang, Shengfa Ye, Chen‐Ho Tung, Li‐Zhu Wu. Tracking an Fe V (O) Intermediate for Water Oxidation in Water. Angewandte Chemie International Edition 2023, 62 (36) https://doi.org/10.1002/anie.202308192
    15. Yuxian Fan, Xiang Xue, Lingyue Zhu, Yuwei Qin, Dandan Yuan, Di Gu, Baohui Wang. The state-of-the-art in the electroreduction of NO x for the production of ammonia in aqueous and nonaqueous media at ambient conditions: a review. New Journal of Chemistry 2023, 47 (13) , 6018-6040. https://doi.org/10.1039/D2NJ06362J
    16. Shujiao Yang, Xialiang Li, Yifan Li, Yabo Wang, Xiaotong Jin, Lingshuang Qin, Wei Zhang, Rui Cao. Effect of Proton Transfer on Electrocatalytic Water Oxidation by Manganese Phosphates. Angewandte Chemie 2023, 135 (1) https://doi.org/10.1002/ange.202215594
    17. Shujiao Yang, Xialiang Li, Yifan Li, Yabo Wang, Xiaotong Jin, Lingshuang Qin, Wei Zhang, Rui Cao. Effect of Proton Transfer on Electrocatalytic Water Oxidation by Manganese Phosphates. Angewandte Chemie International Edition 2023, 62 (1) https://doi.org/10.1002/anie.202215594
    18. Xueqing Gao, Xiaomeng Liu, Shujiao Yang, Wei Zhang, Haiping Lin, Rui Cao. Black phosphorus incorporated cobalt oxide: Biomimetic channels for electrocatalytic water oxidation. Chinese Journal of Catalysis 2022, 43 (4) , 1123-1130. https://doi.org/10.1016/S1872-2067(21)63937-2
    19. Rachel E. Bangle, Jenny Schneider, Quentin Loague, Matthew Kessinger, Andressa V. Müller, Gerald J. Meyer. Free Energy Dependencies for Interfacial Electron Transfer from Tin-Doped Indium Oxide (ITO) to Molecular Photoredox Catalysts. ECS Journal of Solid State Science and Technology 2022, 11 (2) , 025003. https://doi.org/10.1149/2162-8777/ac5169
    20. Jesús A. Luque-Urrutia, Jayneil M. Kamdar, Douglas B. Grotjahn, Miquel Solà, Albert Poater. Understanding the performance of a bisphosphonate Ru water oxidation catalyst. Dalton Transactions 2020, 49 (40) , 14052-14060. https://doi.org/10.1039/D0DT02253E
    21. Bruno M. Aramburu-Trošelj, Rachel E. Bangle, Gerald J. Meyer. Solvent influence on non-adiabatic interfacial electron transfer at conductive oxide electrolyte interfaces. The Journal of Chemical Physics 2020, 153 (13) https://doi.org/10.1063/5.0023766
    22. Zhaohua Miao, Doudou Huang, Yichuan Wang, Wei‐Jian Li, Linxin Fan, Jingguo Wang, Yan Ma, Qingliang Zhao, Zhengbao Zha. Safe‐by‐Design Exfoliation of Niobium Diselenide Atomic Crystals as a Theory‐Oriented 2D Nanoagent from Anti‐Inflammation to Antitumor. Advanced Functional Materials 2020, 30 (40) https://doi.org/10.1002/adfm.202001593
    23. Gentaro Sakamoto, Hiroyasu Tabe, Yusuke Yamada. Immobilization of Ir(OH)3 Nanoparticles in Mesospaces of Al-SiO2 Nanoparticles Assembly to Enhance Stability for Photocatalytic Water Oxidation. Catalysts 2020, 10 (9) , 1015. https://doi.org/10.3390/catal10091015

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    MENDELEY PAIRING EXPIRED
    Your Mendeley pairing has expired. Please reconnect