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Title: The role of proton coupled electron transfer in water oxidation

Journal Article · · Energy & Environmental Science
DOI:https://doi.org/10.1039/C2EE03311A· OSTI ID:1387113

Water oxidation is a key half reaction in energy conversion schemes based on solar fuels and targets such as light driven water splitting or carbon dioxide reduction into CO, other oxygenates, or hydrocarbons. Carrying out these reactions at rates that exceed the rate of solar insolation for the extended periods of time required for useful applications presents a major challenge. Water oxidation is the key “other” half reaction in these schemes and it is dominated by PCET given its multi-electron, multi-proton character, 2H2O → O2 + 4e- + 4H+. Identification of PCET was an offshoot of experiments designed to investigate energy conversion by electron transfer quenching of molecular excited states. The concepts “redox potential leveling” and concerted electron–proton transfer came from measurements on stepwise oxidation of cis-RuII(bpy)2(py)(OH2)2+ to RuIV(bpy)2(py)(O)2+. The Ru “blue dimer”, cis,cis-(bpy)2(H2O)RuORu(OH2)(bpy)24+, was the first designed catalyst for water oxidation. It undergoes oxidative activation by PCET to give the transient (bpy)2(O)RuVORuV(O)(bpy)24+, O-atom attack on water to give a peroxidic intermediate, and further oxidation and O2 release. More recently, a class of single site water oxidation catalysts has been identified, e.g., Ru(tpy)(bpm)(OH2)2+ (tpy is 2,2':6',2''-terpyridine; bpm is 2,2'-bipyrimidine). They undergo stepwise PCET oxidation to RuIV=O2+ or RuV(O)3+ followed by O-atom transfer with formation of peroxidic intermediates which undergo further oxidation and O2 release. PCET plays a key role in the three zones of water oxidation reactivity: oxidative activation, O•••O bond formation, oxidation and O2 release from peroxidic intermediates. Similar schemes have been identified for electrocatalytic water oxidation on oxide electrode surfaces based on phosphonated derivatives such as [Ru(Mebimpy)(4,4'-(PO3H2CH2)2bpy)(OH2)]2+. A PCET barrier to RuIII–OH2+ → RuIV=O2+ oxidation arises from the large difference in pKa values between RuIII–OH2+ and RuIV(OH)3+. On oxide surfaces this oxidation occurs by multiple pathways. Kinetic, mechanistic, and DFT results on single site catalysts reveal a new pathway for the O•••O bond forming step (Atom-Proton Transfer, APT), significant rate enhancements by added proton acceptor bases, and accelerated water oxidation in propylene carbonate as solvent with water added as a stoichiometric reagent. Lessons learned about water oxidation and the role of PCET and concerted pathways appear to have direct relevance for water oxidation in Photosystem II (PSII) with PSII a spectacular example of PCET in action. This includes a key role for Multiple Site-Electron Proton Transfer in oxidative activation of the Oxygen Evolving Complex (OEC) in the S0 → S1 transition in the Kok cycle.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Center for Solar Fuels (UNC EFRC)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
DOE Contract Number:
SC0001011
OSTI ID:
1387113
Journal Information:
Energy & Environmental Science, Vol. 5, Issue 7; Related Information: 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; ISSN 1754-5692
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English

References (87)

Single-Site, Catalytic Water Oxidation on Oxide Surfaces
  • Chen, Zuofeng; Concepcion, Javier J.; Jurss, Jonah W.
  • Journal of the American Chemical Society, Vol. 131, Issue 43, p. 15580-15581 https://doi.org/10.1021/ja906391w
journal November 2009
Interfacial Electron Transfer Dynamics for [Ru(bpy) 2 ((4,4′-PO 3 H 2 ) 2 bpy)] 2+ Sensitized TiO 2 in a Dye-Sensitized Photoelectrosynthesis Cell: Factors Influencing Efficiency and Dynamics journal March 2011
Photosensitized decomposition of some cobalt ammines journal October 1968
Catalytic Water Oxidation by Single-Site Ruthenium Catalysts journal February 2010
Electrochemical Photolysis of Water at a Semiconductor Electrode journal July 1972
Mono- and Bis-(2,2'-bipyridine) and -(1,10-phenanthroline) Chelates of Ruthenium and Osmium. II. Bischelates of Bivalent and Tervalent Ruthenium journal January 1963
Powering the planet: Chemical challenges in solar energy utilization journal October 2006
Platinum Chromophore-Based Systems for Photoinduced Charge Separation:  A Molecular Design Approach for Artificial Photosynthesis journal October 2005
Photodriven heterogeneous charge transfer with transition-metal compounds anchored to TiO 2 semiconductor surfaces journal January 2009
Distinguishing Homogeneous from Heterogeneous Catalysis in Electrode-Driven Water Oxidation with Molecular Iridium Complexes journal July 2011
Mechanistic Implications of Proton Transfer Coupled to Electron Transfer journal October 2001
Oxidizing water two ways journal September 2011
Nonaqueous Catalytic Water Oxidation journal December 2010
Role of D1-His190 in the Proton-Coupled Oxidation of Tyrosine Y Z in Manganese-Depleted Photosystem II journal September 1999
Electron transfer quenching of the luminescent excited state of tris(2,2'-bipyridine)ruthenium(II). Flash photolysis relaxation technique for measuring the rates of very rapid electron transfer reactions journal July 1974
Stability and electrocatalytic activity of the oxo-bridged dimer [(bpy)2(H2O)RuORu(OH2)(bpy)2]4+ in basic solutions journal June 1986
Photochemistry of complex ions. VI. Aqueous thiocyanatopentaamminechromium(III) journal February 1969
Cyanobacterial photosystem II at 2.9-Å resolution and the role of quinones, lipids, channels and chloride journal February 2009
Photochemistry of transition metal complexes. Mechanism and efficiency of energy conversion by electron-transfer quenching journal May 1975
Pathways for water oxidation catalyzed by the (.mu.-oxo)bis[aquabis(bipyridine)ruthenium](4+) ion journal March 1992
Redox properties of the oxo-bridged osmium dimer [(bpy)2(OH2)OsIIIOOsIV(OH)(bpy)2]4+. Implications for the oxidation of water to oxygen journal April 1986
Concerted and Stepwise Proton-Coupled Electron Transfers in Aquo/Hydroxo Complex Couples in Water: Oxidative Electrochemistry of [Os II (bpy) 2 (py)(OH 2 )] 2+ journal January 2009
An Efficient and Selective Photocatalytic System for the Oxidation of Sulfides to Sulfoxides journal February 2003
Quantum mechanical study of the oxidation pathway of the oxygen-evolving catalyst, [(bpy)2(H2O)RuIII-O-RuIII(H2O)(bpy)2]+4 journal January 2001
Energy Conversion in Natural and Artificial Photosynthesis journal May 2010
Proton-Coupled Electron Transfer journal November 2007
Mechanism of Water Oxidation Catalyzed by the μ-Oxo Dimer [(bpy) 2 (OH 2 )Ru III ORu III (OH 2 )(bpy) 2 ] 4+ journal August 1997
Electronic Structure of the Water Oxidation Catalyst cis , cis -[(bpy) 2 (H 2 O)Ru III ORu III (OH 2 )(bpy) 2 ] 4+ , The Blue Dimer journal January 2012
Concerted O atom-proton transfer in the O--O bond forming step in water oxidation journal April 2010
Tunable single-site ruthenium catalysts for efficient water oxidation journal January 2011
Crystal structure of oxygen-evolving photosystem II at a resolution of 1.9 Å journal April 2011
Towards complete cofactor arrangement in the 3.0 Å resolution structure of photosystem II journal December 2005
Low-barrier hydrogen bond plays key role in active photosystem II — A new model for photosynthetic water oxidation journal June 2007
The Remarkable Reactivity of High Oxidation State Ruthenium and Osmium Polypyridyl Complexes journal December 2003
Oxygen transfer in the oxidation of triphenylphosphine by (bpy)2pyRuO2+ journal May 1981
Proton-coupled electron transfer between [Ru(bpy)2(py)OH2]2+ and [Ru(bpy)2(py)O]2+. A solvent isotope effect (kH2O/kD2O) of 16.1 journal May 1981
The Mechanism of Water Oxidation: From Electrolysis via Homogeneous to Biological Catalysis journal June 2010
Where Water Is Oxidized to Dioxygen: Structure of the Photosynthetic Mn4Ca Cluster journal November 2006
Structure and redox properties of the water-oxidation catalyst [(bpy)2(OH2)RuORu(OH2)(bpy)2]4+ journal June 1985
Model Proton-Coupled Electron Transfer Reactions in Solution:  Predictions of Rates, Mechanisms, and Kinetic Isotope Effects journal October 2000
Chemical and photochemical oxidation of organic substrates by ruthenium aqua complexes with water as an oxygen source journal January 2011
Oxobis(2,2'-bipyridine)pyridineruthenium(IV) ion, [(bpy)2(py)Ru:O]2+ journal May 1978
Stoichiometric Photoisomerization of Mononuclear Ruthenium(II) Monoaquo Complexes Controlling Redox Properties and Water Oxidation Catalysis journal June 2011
Solar Energy Supply and Storage for the Legacy and Nonlegacy Worlds journal November 2010
Tris (2,2'-bipyridine)ruthenium(II) sensitized reactions of some oxalato complexes journal August 1973
Surface Catalysis of Water Oxidation by the Blue Ruthenium Dimer journal May 2010
Making solar fuels by artificial photosynthesis journal March 2011
Oxygen atom transfer in the oxidations of dimethyl sulfide and dimethyl sulfoxide by bis(bipyridine)oxo(pyridine)ruthenium(2+) journal March 1987
The Possible Role of Proton-Coupled Electron Transfer (PCET) in Water Oxidation by Photosystem II journal July 2007
Architecture of the Photosynthetic Oxygen-Evolving Center journal March 2004
Mechanisms of Surface Electron Transfer. Proton-Coupled Electron Transfer journal December 1998
Molecular water-oxidation catalysts for photoelectrochemical cells journal January 2009
Artificial photosynthetic systems. Using light and water to provide electrons and protons for the synthesis of a fuel journal January 2011
Highly efficient photocatalytic oxygenation reactions using water as an oxygen source journal November 2010
Involvement of Histidine 190 on the D1 Protein in Electron/Proton Transfer Reactions on the Donor Side of Photosystem II journal October 1998
Proton and hydrogen currents in photosynthetic water oxidation journal May 2000
Concerted proton-coupled electron transfers in aquo/hydroxo/oxo metal complexes: Electrochemistry of [OsII(bpy)2py(OH2)]2+ in water journal July 2009
Kinetic relaxation measurement of rapid electron transfer reactions by flash photolysis. Conversion of light energy into chemical energy using the tris(2,2'-bipyridine)ruthenium(3+)-tris(2,2'-bipyridine)ruthenium(2+*) couple journal August 1975
One Site is Enough. Catalytic Water Oxidation by [Ru(tpy)(bpm)(OH 2 )] 2+ and [Ru(tpy)(bpz)(OH 2 )] 2+ journal December 2008
Coupled electron transfers in artificial photosynthesis journal October 2007
Molecular Approaches to Solar Energy Conversion with Coordination Compounds Anchored to Semiconductor Surfaces journal October 2005
A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films journal October 1991
Proton-coupled electron transfer at modified electrodes by multiple pathways journal December 2011
Catalytic water oxidation on derivatized nanoITO journal January 2010
Making Oxygen with Ruthenium Complexes journal December 2009
Catalytic oxidation of water by an oxo-bridged ruthenium dimer journal July 1982
Estimation of excited-state redox potentials by electron-transfer quenching. Application of electron-transfer theory to excited-state redox processes journal August 1979
Mechanism of Water Oxidation by Single-Site Ruthenium Complex Catalysts
  • 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
journal February 2010
A Model for the Photosystem II Reaction Center Core Including the Structure of the Primary Donor P 680 , journal January 1996
Ru(II) polypyridine complexes: photophysics, photochemistry, eletrochemistry, and chemiluminescence journal March 1988
Integrating proton coupled electron transfer (PCET) and excited states journal November 2010
Systematic Investigation of the Catalytic Cycle of a Single Site Ruthenium Oxygen Evolving Complex Using Density Functional Theory journal July 2011
COOPERATION OF CHARGES IN PHOTOSYNTHETIC O 2 EVOLUTION–I. A LINEAR FOUR STEP MECHANISM journal June 1970
Chemical approaches to artificial photosynthesis journal May 1989
Colossal kinetic isotope effects in proton-coupled electron transfer journal August 2004
Catalytic Mechanism of Water Oxidation with Single-Site Ruthenium–Heteropolytungstate Complexes journal August 2011
Mediator-assisted water oxidation by the ruthenium "blue dimer" cis,cis-[(bpy)2(H2O)RuORu(OH2)(bpy)2]4+ journal November 2008
Water Oxidation by a Mononuclear Ruthenium Catalyst: Characterization of the Intermediates journal September 2011
Chemical Approaches to Artificial Photosynthesis. 2 journal October 2005
Solar Energy Conversion by Dye-Sensitized Photovoltaic Cells journal October 2005
Recent Advances in Sensitized Mesoscopic Solar Cells journal November 2009
Photochemical Conversion of Solar Energy journal February 2008
Properties of the oxo/aqua system (bpy)2(py)RuO2+/(bpy)2(py)Ru(OH2)2+ journal February 1981
Mechanisms of Water Oxidation from the Blue Dimer to Photosystem II journal March 2008
Kinetic and Energetic Paradigms for Dye-Sensitized Solar Cells: Moving from the Ideal to the Real journal November 2009
A Metalloradical Mechanism for the Generation of Oxygen from Water in Photosynthesis journal September 1997
Lumenal side histidine mutations in the D1 protein of photosystem II affect donor side electron transfer in Chlamydomonas reinhardtii journal May 1994