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Title: Base-enhanced catalytic water oxidation by a carboxylate–bipyridine Ru(II) complex

Abstract

In aqueous solution above pH 2.4 with 4% (vol/vol) CH 3CN, the complex [Ru II(bda)(isoq) 2] (bda is 2,2'-bipyridine-6,6'-dicarboxylate; isoq is isoquinoline) exists as the open-arm chelate, [Ru II(CO 2-bpy-CO 2 $$-$$)(isoq) 2(NCCH 3)], as shown by 1H and 13C-NMR, X-ray crystallography, and pH titrations. Rates of water oxidation with the open-arm chelate are remarkably enhanced by added proton acceptor bases, as measured by cyclic voltammetry (CV). In 1.0 M PO 4 3–, the calculated half-time for water oxidation is ~7 μs. In conclusion, the key to the rate accelerations with added bases is direct involvement of the buffer base in either atom–proton transfer (APT) or concerted electron–proton transfer (EPT) pathways.

Authors:
 [1];  [2];  [2];  [2];  [3];  [2];  [2];  [2]
  1. Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry; Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry
  3. Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry; Univ. of South Carolina, Columbia, SC (United States). Dept. of Chemistry and Biochemistry
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Solar Fuels (UNC EFRC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Contributing Org.:
UNC partners with University of North Carolina (lead); Duke University; University of Florida; Georgia Institute of Technology; University; North Carolina Central University; Research Triangle Institute
OSTI Identifier:
1210509
Grant/Contract Number:  
SC0001011; CHE-0957215
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 112; Journal Issue: 16; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (homogeneous); catalysis (heterogeneous); solar (photovoltaic); solar (fuels); photosynthesis (natural and artificial); hydrogen and fuel cells; electrodes - solar, charge transport; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); Ru polypyridyl complexes; electrocatalysis; solar energy; water oxidation catalysis; water splitting

Citation Formats

Song, Na, Concepcion, Javier J., Binstead, Robert A., Rudd, Jennifer A., Vannucci, Aaron K., Dares, Christopher J., Coggins, Michael K., and Meyer, Thomas J. Base-enhanced catalytic water oxidation by a carboxylate–bipyridine Ru(II) complex. United States: N. p., 2015. Web. doi:10.1073/pnas.1500245112.
Song, Na, Concepcion, Javier J., Binstead, Robert A., Rudd, Jennifer A., Vannucci, Aaron K., Dares, Christopher J., Coggins, Michael K., & Meyer, Thomas J. Base-enhanced catalytic water oxidation by a carboxylate–bipyridine Ru(II) complex. United States. https://doi.org/10.1073/pnas.1500245112
Song, Na, Concepcion, Javier J., Binstead, Robert A., Rudd, Jennifer A., Vannucci, Aaron K., Dares, Christopher J., Coggins, Michael K., and Meyer, Thomas J. Mon . "Base-enhanced catalytic water oxidation by a carboxylate–bipyridine Ru(II) complex". United States. https://doi.org/10.1073/pnas.1500245112. https://www.osti.gov/servlets/purl/1210509.
@article{osti_1210509,
title = {Base-enhanced catalytic water oxidation by a carboxylate–bipyridine Ru(II) complex},
author = {Song, Na and Concepcion, Javier J. and Binstead, Robert A. and Rudd, Jennifer A. and Vannucci, Aaron K. and Dares, Christopher J. and Coggins, Michael K. and Meyer, Thomas J.},
abstractNote = {In aqueous solution above pH 2.4 with 4% (vol/vol) CH3CN, the complex [RuII(bda)(isoq)2] (bda is 2,2'-bipyridine-6,6'-dicarboxylate; isoq is isoquinoline) exists as the open-arm chelate, [RuII(CO2-bpy-CO2$-$)(isoq)2(NCCH3)], as shown by 1H and 13C-NMR, X-ray crystallography, and pH titrations. Rates of water oxidation with the open-arm chelate are remarkably enhanced by added proton acceptor bases, as measured by cyclic voltammetry (CV). In 1.0 M PO43–, the calculated half-time for water oxidation is ~7 μs. In conclusion, the key to the rate accelerations with added bases is direct involvement of the buffer base in either atom–proton transfer (APT) or concerted electron–proton transfer (EPT) pathways.},
doi = {10.1073/pnas.1500245112},
url = {https://www.osti.gov/biblio/1210509}, journal = {Proceedings of the National Academy of Sciences of the United States of America},
issn = {0027-8424},
number = 16,
volume = 112,
place = {United States},
year = {2015},
month = {4}
}

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Works referenced in this record:

Precursor Transformation during Molecular Oxidation Catalysis with Organometallic Iridium Complexes
journal, July 2013


Ligand Exchange and Spin State Equilibria of Fe II (N4Py) and Related Complexes in Aqueous Media
journal, December 2011


Structure–Property Relationships in Phosphonate-Derivatized, Ru II Polypyridyl Dyes on Metal Oxide Surfaces in an Aqueous Environment
journal, July 2012


Electrocatalysts for O2 reduction
journal, November 1984


One Site is Enough. Catalytic Water Oxidation by [Ru(tpy)(bpm)(OH 2 )] 2+ and [Ru(tpy)(bpz)(OH 2 )] 2+
journal, December 2008


Electrocatalytic Oxidation of Tyrosine by Parallel Rate-Limiting Proton Transfer and Multisite Electron−Proton Transfer
journal, August 2006


Rapid catalyticwateroxidation by a single site, Rucarbenecatalyst
journal, January 2011


Proton-Coupled Electron Transfer
journal, April 2012


Efficient water oxidation catalyzed by homogeneous cationic cobalt porphyrins with critical roles for the buffer base
journal, September 2013


Catalytic water oxidation on derivatized nanoITO
journal, January 2010


A Ru(II) Bis-terpyridine-like Complex that Catalyzes Water Oxidation: The Influence of Steric Strain
journal, August 2013


The role of proton coupled electron transfer in water oxidation
journal, January 2012


Divide and conquer
journal, April 2013


Proton-Coupled Electron Transfer
journal, November 2007


Concerted O atom-proton transfer in the O--O bond forming step in water oxidation
journal, April 2010


Mechanism of Water Oxidation by Single-Site Ruthenium Complex Catalysts
journal, February 2010

  • Concepcion, Javier J.; Tsai, Ming-Kang; Muckerman, James T.
  • Journal of the American Chemical Society, Vol. 132, Issue 5, p. 1545-1557
  • https://doi.org/10.1021/ja904906v

Surface Activation of Electrocatalysis at Oxide Electrodes. Concerted Electron−Proton Transfer
journal, March 2011


Theoretical study of catalytic mechanism for single-site water oxidation process
journal, May 2012


Crossing the divide between homogeneous and heterogeneous catalysis in water oxidation
journal, November 2013


A soluble copper–bipyridine water-oxidation electrocatalyst
journal, May 2012


Fast Water Oxidation Using Iron
journal, August 2010


In Situ Formation of an Oxygen-Evolving Catalyst in Neutral Water Containing Phosphate and Co2+
journal, August 2008


Water Oxidation with Mononuclear Ruthenium(II) Polypyridine Complexes Involving a Direct Ru IV ═O Pathway in Neutral and Alkaline Media
journal, July 2013


Homogeneous water oxidation catalysts containing a single metal site
journal, January 2013


New Powerful and Oxidatively Rugged Dinuclear Ru Water Oxidation Catalyst: Control of Mechanistic Pathways by Tailored Ligand Design
journal, December 2013


Catalytic Mechanism of Water Oxidation with Single-Site Ruthenium–Heteropolytungstate Complexes
journal, August 2011


A molecular ruthenium catalyst with water-oxidation activity comparable to that of photosystem II
journal, March 2012


Surface Catalysis of Water Oxidation by the Blue Ruthenium Dimer
journal, May 2010


Highly efficient and robust molecular ruthenium catalysts for water oxidation
journal, July 2012


Proton-Coupled Electron Transfers: pH-Dependent Driving Forces? Fundamentals and Artifacts
journal, September 2013


Insight into Water Oxidation by Mononuclear Polypyridyl Ru Catalysts
journal, March 2010


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    Water Oxidation by Ruthenium Complexes Incorporating Multifunctional Bipyridyl Diphosphonate Ligands
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    Electrochemical Formation of Fe V (O) and Mechanism of Its Reaction with Water During O−O Bond Formation
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    Catalyst–solvent interactions in a dinuclear Ru-based water oxidation catalyst
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    Crystal structures of three 4-substituted-2,2′-bipyridines synthesized by Sonogashira and Suzuki–Miyaura cross-coupling reactions
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    Water Oxidation by Ruthenium Complexes Incorporating Multifunctional Bipyridyl Diphosphonate Ligands
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    Electrochemical Formation of Fe V (O) and Mechanism of Its Reaction with Water During O−O Bond Formation
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    Characterization of a trinuclear ruthenium species in catalytic water oxidation by Ru(bda)(pic) 2 in neutral media
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    Catalyst–solvent interactions in a dinuclear Ru-based water oxidation catalyst
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    journal, August 2018


    Efficient BiVO 4 Photoanodes by Postsynthetic Treatment: Remarkable Improvements in Photoelectrochemical Performance from Facile Borate Modification
    journal, December 2019


    Electrocatalytic Water Oxidation by Mononuclear Cu(II) Aliphatic Tetraamine Complexes
    journal, March 2019


    Mono‐/Multinuclear Water Oxidation Catalysts
    journal, June 2019


    Mechanistic Insights into Light-Activated Catalysis for Water Oxidation: Mechanistic Insights into Light-Activated Catalysis for Water Oxidation
    journal, January 2019


    Direct oxygen isotope effect identifies the rate-determining step of electrocatalytic OER at an oxidic surface
    journal, November 2018


    How to make an efficient and robust molecular catalyst for water oxidation
    journal, January 2017


    Mechanisms of molecular water oxidation in solution and on oxide surfaces
    journal, January 2017


    O–O bond formation in ruthenium-catalyzed water oxidation: single-site nucleophilic attack vs. O–O radical coupling
    journal, January 2017


    Artificial photosynthesis: opportunities and challenges of molecular catalysts
    journal, January 2019


    Kinetics and mechanisms of catalytic water oxidation
    journal, January 2019


    Proton coupled electron transfer from Co 3 O 4 nanoparticles to photogenerated Ru(bpy) 3 3+ : base catalysis and buffer effect
    journal, January 2018


    Homogenous electrochemical water oxidation by a nickel( ii ) complex based on a macrocyclic N-heterocyclic carbene/pyridine hybrid ligand
    journal, January 2019


    Structural evolution of the Ru-bms complex to the real water oxidation catalyst of Ru-bda: the bite angle matters
    journal, January 2020