Hydrogen Bonding Rescues Overpotential in Seven-Coordinated Ru Water Oxidation Catalysts
Abstract
In this paper, we describe the synthesis, structural characterization, and redox properties of two new Ru complexes containing the dianionic potentially pentadentate [2,2':6',2"-terpyridine]-6,6"-dicarboxylate (tda2–) ligand that coordinates Ru at the equatorial plane and with additional pyridine or dmso acting as monondentate ligand in the axial positions: [RuII(tda-κ-N3O)(py)(dmso)], 1II and [RuIII(tda-κ-N3O2)(py)(H2O)ax]+, 2III(H2O)+. Complex 1II has been characterized by single-crystal XRD in the solid state and in solution by NMR spectroscopy. The redox properties of 1II and 2III(H2O)+ have been thoroughly investigated by means of cyclic voltammetry and differential pulse voltammetry. Complex 2II(H2O) displays poor catalytic activity with regard to the oxidation of water to dioxygen, and its properties have been analyzed on the basis of foot of the wave analysis and catalytic Tafel plots. The activity of 2II(H2O) has been compared with related water oxidation catalysts (WOCs) previously described in the literature. Despite its moderate activity, 2II(H2O) constitutes the cornerstone that has triggered the rationalization of the different factors that govern overpotentials as well as efficiencies in molecular WOCs. The present work uncovers the interplay between different parameters, namely, coordination number, number of anionic groups bonded to the first-coordination sphere of the metal center, water oxidation catalysis overpotential, pKa and hydrogenmore »
- Authors:
-
[1];
[5]
- Barcelona Institute of Science and Technology (BIST), Tarragona (Spain); Univ. Rovira i Virgili, Tarragona (Spain)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Barcelona Institute of Science and Technology (BIST), Tarragona (Spain)
- Univ. Autonoma de Barcelona, Barcelona (Spain)
- Barcelona Institute of Science and Technology (BIST), Tarragona (Spain); Univ. Autonoma de Barcelona, Barcelona (Spain)
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1405933
- Report Number(s):
- BNL-114431-2017-JA
Journal ID: ISSN 2155-5435; R&D Project: CO026; KC0304030
- Grant/Contract Number:
- SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Catalysis
- Additional Journal Information:
- Journal Volume: 7; Journal Issue: 10; Journal ID: ISSN 2155-5435
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; electrocatalysis; hydrogen bonding; redox properties; Ru complexes; seven coordination; water oxidation catalysis; water splitting
Citation Formats
Matheu, Roc, Ertem, Mehmed Z., Gimbert-Surinach, Carolina, Benet-Buchholz, Jordi, Sala, Xavier, and Llobet, Antoni. Hydrogen Bonding Rescues Overpotential in Seven-Coordinated Ru Water Oxidation Catalysts. United States: N. p., 2017.
Web. doi:10.1021/acscatal.7b01860.
Matheu, Roc, Ertem, Mehmed Z., Gimbert-Surinach, Carolina, Benet-Buchholz, Jordi, Sala, Xavier, & Llobet, Antoni. Hydrogen Bonding Rescues Overpotential in Seven-Coordinated Ru Water Oxidation Catalysts. United States. https://doi.org/10.1021/acscatal.7b01860
Matheu, Roc, Ertem, Mehmed Z., Gimbert-Surinach, Carolina, Benet-Buchholz, Jordi, Sala, Xavier, and Llobet, Antoni. Tue .
"Hydrogen Bonding Rescues Overpotential in Seven-Coordinated Ru Water Oxidation Catalysts". United States. https://doi.org/10.1021/acscatal.7b01860. https://www.osti.gov/servlets/purl/1405933.
@article{osti_1405933,
title = {Hydrogen Bonding Rescues Overpotential in Seven-Coordinated Ru Water Oxidation Catalysts},
author = {Matheu, Roc and Ertem, Mehmed Z. and Gimbert-Surinach, Carolina and Benet-Buchholz, Jordi and Sala, Xavier and Llobet, Antoni},
abstractNote = {In this paper, we describe the synthesis, structural characterization, and redox properties of two new Ru complexes containing the dianionic potentially pentadentate [2,2':6',2"-terpyridine]-6,6"-dicarboxylate (tda2–) ligand that coordinates Ru at the equatorial plane and with additional pyridine or dmso acting as monondentate ligand in the axial positions: [RuII(tda-κ-N3O)(py)(dmso)], 1II and [RuIII(tda-κ-N3O2)(py)(H2O)ax]+, 2III(H2O)+. Complex 1II has been characterized by single-crystal XRD in the solid state and in solution by NMR spectroscopy. The redox properties of 1II and 2III(H2O)+ have been thoroughly investigated by means of cyclic voltammetry and differential pulse voltammetry. Complex 2II(H2O) displays poor catalytic activity with regard to the oxidation of water to dioxygen, and its properties have been analyzed on the basis of foot of the wave analysis and catalytic Tafel plots. The activity of 2II(H2O) has been compared with related water oxidation catalysts (WOCs) previously described in the literature. Despite its moderate activity, 2II(H2O) constitutes the cornerstone that has triggered the rationalization of the different factors that govern overpotentials as well as efficiencies in molecular WOCs. The present work uncovers the interplay between different parameters, namely, coordination number, number of anionic groups bonded to the first-coordination sphere of the metal center, water oxidation catalysis overpotential, pKa and hydrogen bonding, and the performance of a given WOC. It thus establishes the basic principles for the design of efficient WOCs operating at low overpotentials.},
doi = {10.1021/acscatal.7b01860},
journal = {ACS Catalysis},
number = 10,
volume = 7,
place = {United States},
year = {Tue Aug 15 00:00:00 EDT 2017},
month = {Tue Aug 15 00:00:00 EDT 2017}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 45 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Will Solar-Driven Water-Splitting Devices See the Light of Day?
journal, September 2013
- McKone, James R.; Lewis, Nathan S.; Gray, Harry B.
- Chemistry of Materials, Vol. 26, Issue 1
Research opportunities to advance solar energy utilization
journal, January 2016
- Lewis, N. S.
- Science, Vol. 351, Issue 6271
Benchmarking Hydrogen Evolving Reaction and Oxygen Evolving Reaction Electrocatalysts for Solar Water Splitting Devices
journal, March 2015
- McCrory, Charles C. L.; Jung, Suho; Ferrer, Ivonne M.
- Journal of the American Chemical Society, Vol. 137, Issue 13
A soluble copper–bipyridine water-oxidation electrocatalyst
journal, May 2012
- Barnett, Shoshanna M.; Goldberg, Karen I.; Mayer, James M.
- Nature Chemistry, Vol. 4, Issue 6
Fast Water Oxidation Using Iron
journal, August 2010
- Ellis, W. Chadwick; McDaniel, Neal D.; Bernhard, Stefan
- Journal of the American Chemical Society, Vol. 132, Issue 32
Molecular Water Oxidation Mechanisms Followed by Transition Metals: State of the Art
journal, December 2013
- Sala, Xavier; Maji, Somnath; Bofill, Roger
- Accounts of Chemical Research, Vol. 47, Issue 2
Electrochemical and Resonance Raman Spectroscopic Studies of Water-Oxidizing Ruthenium Terpyridyl-Bipyridyl Complexes
journal, December 2016
- Keidel, Anke; López, Isidoro; Staffa, Jana
- ChemSusChem, Vol. 10, Issue 3
Molecular Catalysts for Water Oxidation
journal, July 2015
- Blakemore, James D.; Crabtree, Robert H.; Brudvig, Gary W.
- Chemical Reviews, Vol. 115, Issue 23
Frontiers of water oxidation: the quest for true catalysts
journal, January 2017
- Li, J.; Güttinger, R.; Moré, R.
- Chemical Society Reviews, Vol. 46, Issue 20
A molecular catalyst for water oxidation that binds to metal oxide surfaces
journal, March 2015
- Sheehan, Stafford W.; Thomsen, Julianne M.; Hintermair, Ulrich
- Nature Communications, Vol. 6, Issue 1
A pentanuclear iron catalyst designed for water oxidation
journal, February 2016
- Okamura, Masaya; Kondo, Mio; Kuga, Reiko
- Nature, Vol. 530, Issue 7591
A New Ru Complex Capable of Catalytically Oxidizing Water to Molecular Dioxygen
journal, June 2004
- Sens, Cristina; Romero, Isabel; Rodríguez, Montserrat
- Journal of the American Chemical Society, Vol. 126, Issue 25
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
New Powerful and Oxidatively Rugged Dinuclear Ru Water Oxidation Catalyst: Control of Mechanistic Pathways by Tailored Ligand Design
journal, December 2013
- Neudeck, Sven; Maji, Somnath; López, Isidoro
- Journal of the American Chemical Society, Vol. 136, Issue 1
Electronic Modification of the [Ru II (tpy)(bpy)(OH 2 )] 2+ Scaffold: Effects on Catalytic Water Oxidation
journal, November 2010
- Wasylenko, Derek J.; Ganesamoorthy, Chelladurai; Henderson, Matthew A.
- Journal of the American Chemical Society, Vol. 132, Issue 45
Water Oxidation by a Mononuclear Ruthenium Catalyst: Characterization of the Intermediates
journal, September 2011
- Polyansky, Dmitry E.; Muckerman, James T.; Rochford, Jonathan
- Journal of the American Chemical Society, Vol. 133, Issue 37
Manipulating the Rate-Limiting Step in Water Oxidation Catalysis by Ruthenium Bipyridine–Dicarboxylate Complexes
journal, November 2016
- Shaffer, David W.; Xie, Yan; Szalda, David J.
- Inorganic Chemistry, Vol. 55, Issue 22
A supramolecular ruthenium macrocycle with high catalytic activity for water oxidation that mechanistically mimics photosystem II
journal, May 2016
- Schulze, Marcus; Kunz, Valentin; Frischmann, Peter D.
- Nature Chemistry, Vol. 8, Issue 6
Structural and Spectroscopic Characterization of Reaction Intermediates Involved in a Dinuclear Co–Hbpp Water Oxidation Catalyst
journal, November 2016
- Gimbert-Suriñach, Carolina; Moonshiram, Dooshaye; Francàs, Laia
- Journal of the American Chemical Society, Vol. 138, Issue 47
A molecular ruthenium catalyst with water-oxidation activity comparable to that of photosystem II
journal, March 2012
- Duan, Lele; Bozoglian, Fernando; Mandal, Sukanta
- Nature Chemistry, Vol. 4, Issue 5
Supramolecular Water Oxidation with Ru-bda-Based Catalysts
journal, November 2014
- Richmond, Craig J.; Matheu, Roc; Poater, Albert
- Chemistry - A European Journal, Vol. 20, Issue 52
Highly efficient and robust molecular water oxidation catalysts based on ruthenium complexes
journal, January 2014
- Wang, Lei; Duan, Lele; Wang, Ying
- Chem. Commun., Vol. 50, Issue 85
Intramolecular Proton Transfer Boosts Water Oxidation Catalyzed by a Ru Complex
journal, August 2015
- Matheu, Roc; Ertem, Mehmed Z.; Benet-Buchholz, Jordi
- Journal of the American Chemical Society, Vol. 137, Issue 33
A Million Turnover Molecular Anode for Catalytic Water Oxidation
journal, November 2016
- Creus, Jordi; Matheu, Roc; Peñafiel, Itziar
- Angewandte Chemie International Edition, Vol. 55, Issue 49
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals
journal, July 2007
- Zhao, Yan; Truhlar, Donald G.
- Theoretical Chemistry Accounts, Vol. 120, Issue 1-3
Density Functionals with Broad Applicability in Chemistry
journal, February 2008
- Zhao, Yan; Truhlar, Donald G.
- Accounts of Chemical Research, Vol. 41, Issue 2
Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions
journal, May 2009
- Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
- The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396
Electrochemical parametrization of metal complex redox potentials, using the ruthenium(III)/ruthenium(II) couple to generate a ligand electrochemical series
journal, March 1990
- Lever, A. B. P.
- Inorganic Chemistry, Vol. 29, Issue 6, p. 1271-1285
Can the Disproportion of Oxidation State III Be Favored in RuII−OH2/RuIVO Systems?
journal, March 2006
- Masllorens, Ester; Rodríguez, Montserrat; Romero, Isabel
- Journal of the American Chemical Society, Vol. 128, Issue 16
Foot of the Wave Analysis for Mechanistic Elucidation and Benchmarking Applications in Molecular Water Oxidation Catalysis
journal, November 2016
- Matheu, Roc; Neudeck, Sven; Meyer, Franc
- ChemSusChem, Vol. 9, Issue 23
Turnover Numbers, Turnover Frequencies, and Overpotential in Molecular Catalysis of Electrochemical Reactions. Cyclic Voltammetry and Preparative-Scale Electrolysis
journal, June 2012
- Costentin, Cyrille; Drouet, Samuel; Robert, Marc
- Journal of the American Chemical Society, Vol. 134, Issue 27, p. 11235-11242
Water oxidation catalysis with ligand substituted Ru–bpp type complexes
journal, January 2016
- Roeser, Stephan; Bozoglian, Fernando; Richmond, Craig J.
- Catalysis Science & Technology, Vol. 6, Issue 13
Unraveling the Roles of the Acid Medium, Experimental Probes, and Terminal Oxidant, (NH 4 ) 2 [Ce(NO 3 ) 6 ], in the Study of a Homogeneous Water Oxidation Catalyst
journal, April 2011
- Wasylenko, Derek J.; Ganesamoorthy, Chelladurai; Henderson, Matthew A.
- Inorganic Chemistry, Vol. 50, Issue 8
Single Site Isomeric Ru WOCs with an Electron-Withdrawing Group: Synthesis, Electrochemical Characterization, and Reactivity
journal, December 2015
- Mognon, Lorenzo; Benet-Buchholz, Jordi; Llobet, Antoni
- Inorganic Chemistry, Vol. 54, Issue 24
Catalytic Water Oxidation by Mononuclear Ru Complexes with an Anionic Ancillary Ligand
journal, February 2013
- Tong, Lianpeng; Inge, A. Ken; Duan, Lele
- Inorganic Chemistry, Vol. 52, Issue 5
Immobilization of a molecular catalyst on carbon nanotubes for highly efficient electro-catalytic water oxidation
journal, January 2014
- Li, Fusheng; Li, Lin; Tong, Lianpeng
- Chem. Commun., Vol. 50, Issue 90
The Ru-tpc Water Oxidation Catalyst and Beyond: Water Nucleophilic Attack Pathway versus Radical Coupling Pathway
journal, March 2017
- Fan, Ting; Duan, Lele; Huang, Ping
- ACS Catalysis, Vol. 7, Issue 4
Catalytic Water Oxidation by Ruthenium(II) Quaterpyridine (qpy) Complexes: Evidence for Ruthenium(III) qpy- N , N ′′′-dioxide as the Real Catalysts
journal, October 2014
- Liu, Yingying; Ng, Siu-Mui; Yiu, Shek-Man
- Angewandte Chemie International Edition, Vol. 53, Issue 52
Isolated Seven-Coordinate Ru(IV) Dimer Complex with [HOHOH] − Bridging Ligand as an Intermediate for Catalytic Water Oxidation
journal, August 2009
- Duan, Lele; Fischer, Andreas; Xu, Yunhua
- Journal of the American Chemical Society, Vol. 131, Issue 30
Concerted O atom-proton transfer in the O--O bond forming step in water oxidation
journal, April 2010
- Chen, Z.; Concepcion, J. J.; Hu, X.
- Proceedings of the National Academy of Sciences, Vol. 107, Issue 16, p. 7225-7229
Base-enhanced catalytic water oxidation by a carboxylate–bipyridine Ru(II) complex
journal, April 2015
- Song, Na; Concepcion, Javier J.; Binstead, Robert A.
- Proceedings of the National Academy of Sciences, Vol. 112, Issue 16
Works referencing / citing this record:
Catalytic Oxidation of Water to Dioxygen by Mononuclear Ru Complexes Bearing a 2,6‐Pyridinedicarboxylato Ligand
journal, November 2018
- Hoque, Md Asmaul; Benet‐Buchholz, Jordi; Llobet, Antoni
- ChemSusChem, Vol. 12, Issue 9
Reversible pyrrole-based proton storage/release in ruthenium( ii ) complexes
journal, January 2019
- Zhang, Zheng-Hao; He, Piao; Kang, Shi-Rui
- Chemical Communications, Vol. 55, Issue 97
The development of molecular water oxidation catalysts
journal, April 2019
- Matheu, Roc; Garrido-Barros, Pablo; Gil-Sepulcre, Marcos
- Nature Reviews Chemistry, Vol. 3, Issue 5
Low overpotential water oxidation at neutral pH catalyzed by a copper( ii ) porphyrin
journal, January 2019
- Liu, Yanju; Han, Yongzhen; Zhang, Zongyao
- Chemical Science, Vol. 10, Issue 9
Reversible Decay of Oxygen Evolution Activity of Iridium Catalysts
journal, January 2019
- Tang-Kong, Robert; Chidsey, Chrisopher E. D.; McIntyre, Paul C.
- Journal of The Electrochemical Society, Vol. 166, Issue 14
Universal scaling relations for the rational design of molecular water oxidation catalysts with near-zero overpotential
journal, November 2019
- Craig, Michael John; Coulter, Gabriel; Dolan, Eoin
- Nature Communications, Vol. 10, Issue 1
Strategic Isolation of a Polyoxocation Mimicking Vanadium(V) Oxide Layered-Structure by Stacking of [H2V2O8]4− Anions Bridged by (1,4,7-Triazacyclononane)Co(III) Complexes
journal, August 2018
- Sugiarto, ; Kawamoto, Keisuke; Hayashi, Yoshihito
- Frontiers in Chemistry, Vol. 6
Electrochemically Driven Water Oxidation by a Highly Active Ruthenium‐Based Catalyst
journal, April 2019
- Shatskiy, Andrey; Bardin, Andrey A.; Oschmann, Michael
- ChemSusChem, Vol. 12, Issue 10
Solvent-free aerobic selective oxidation of hydrocarbons catalyzed by porous graphitic carbon encapsulated cobalt composites
journal, January 2018
- Jiang, Yuchen; Zhang, Chenjun; Li, Yue
- New Journal of Chemistry, Vol. 42, Issue 20
Pentanuclear iron catalysts for water oxidation: substituents provide two routes to control onset potentials
journal, January 2019
- Praneeth, Vijayendran K. K.; Kondo, Mio; Okamura, Masaya
- Chemical Science, Vol. 10, Issue 17
An Overview of Significant Achievements in Ruthenium-Based Molecular Water Oxidation Catalysis
journal, January 2019
- Kamdar, Jayneil; Grotjahn, Douglas
- Molecules, Vol. 24, Issue 3