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Title: Water-Nucleophilic Attack Mechanism for the CuII(pyalk)2 Water-Oxidation Catalyst

Journal Article · · ACS Catalysis
ORCiD logo [1];  [1];  [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Yale Univ., New Haven, CT (United States)
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Here, we investigate the mechanism of water oxidation catalyzed by the CuII(pyalk)2 complex, combining density functional theory with experimental measurements of turnover frequencies, UV–visible spectra, H/D kinetic isotope effects (KIEs), electrochemical analysis, and synthesis of a derivative complex. We find that only in the cis form does CuII(pyalk)2 convert water to dioxygen. In a series of alternating chemical and electrochemical steps, the catalyst is activated to form a metal oxyl radical species that undergoes a water-nucleophilic attack defining the rate-limiting step of the reaction. The experimental H/D KIE (3.4) is in agreement with the calculated value (3.7), shown to be determined by deprotonation of the substrate nucleophile upon O–O bond formation. The reported mechanistic findings are particularly valuable for rational design of complexes inspired by CuII(pyalk)2.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Center for Light Energy Activated Redox Processes (LEAP); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Northwestern Univ., Evanston, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
SC0001059
OSTI ID:
1543705
Journal Information:
ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 9 Vol. 8; ISSN 2155-5435
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (68)

Theoretical and Experimental Aspects of Isotope Effects in Chemical Kinetics book December 1956
Construction of Pourbaix Diagrams for Ruthenium-Based Water-Oxidation Catalysts by Density Functional Theory journal November 2012
Single-Site Copper(II) Water Oxidation Electrocatalysis: Rate Enhancements with HPO 4 2− as a Proton Acceptor at pH 8 journal September 2014
Electrocatalytic Water Oxidation by a Dinuclear Copper Complex in a Neutral Aqueous Solution journal February 2015
Quantum Refinement Does Not Support Dinuclear Copper Sites in Crystal Structures of Particulate Methane Monooxygenase journal December 2017
Catalytic Oxygen Evolution from Manganese Complexes with an Oxidation-Resistant N,N,O-Donor Ligand journal October 2016
A Ru-Hbpp-Based Water-Oxidation Catalyst Anchored on Rutile TiO 2 journal April 2009
Foot of the Wave Analysis for Mechanistic Elucidation and Benchmarking Applications in Molecular Water Oxidation Catalysis journal November 2016
Quantum Chemical Modeling of Homogeneous Water Oxidation Catalysis journal October 2017
Efficient diffuse function-augmented basis sets for anion calculations. III. The 3-21+G basis set for first-row elements, Li-F journal October 1983
Treatment of electronic excitations within the adiabatic approximation of time dependent density functional theory journal July 1996
Geometric derivatives of excitation energies using SCF and DFT journal July 1999
Geometric derivatives of density functional theory excitation energies using gradient-corrected functionals journal January 2000
Light-driven water oxidation for solar fuels journal November 2012
DFT flavor of coordination chemistry journal August 2014
A Pyridine Alkoxide Chelate Ligand That Promotes Both Unusually High Oxidation States and Water-Oxidation Catalysis journal February 2017
Molecular Catalysts for Water Oxidation journal July 2015
Electrocatalytic Water Oxidation by a Water-Soluble Copper(II) Complex with a Copper-Bound Carbonate Group Acting as a Potential Proton Shuttle journal October 2017
Mechanism of Manganese-Catalyzed Oxygen Evolution from Experimental and Theoretical Analyses of 18 O Kinetic Isotope Effects journal November 2015
Single Electron Transfer Steps in Water Oxidation Catalysis. Redefining the Mechanistic Scenario journal February 2017
Electrocatalytic Water Oxidation by a Copper(II) Complex of an Oxidation-Resistant Ligand journal April 2017
How to Conceptualize Catalytic Cycles? The Energetic Span Model journal February 2011
Assessment of the Performance of DFT and DFT-D Methods for Describing Distance Dependence of Hydrogen-Bonded Interactions journal December 2010
Density Functional Theory of Open-Shell Systems. The 3d-Series Transition-Metal Atoms and Their Cations journal November 2013
Electrocatalytic Water Oxidation with a Copper(II) Polypeptide Complex journal January 2013
Redox Non-innocent Ligand Controls Water Oxidation Overpotential in a New Family of Mononuclear Cu-Based Efficient Catalysts journal May 2015
Solution Structures of Highly Active Molecular Ir Water-Oxidation Catalysts from Density Functional Theory Combined with High-Energy X-ray Scattering and EXAFS Spectroscopy journal April 2016
Electrocatalytic Water Oxidation by a Homogeneous Copper Catalyst Disfavors Single-Site Mechanisms journal June 2017
Computing Redox Potentials in Solution:  Density Functional Theory as A Tool for Rational Design of Redox Agents journal August 2002
Aqueous Solvation Free Energies of Ions and Ion−Water Clusters Based on an Accurate Value for the Absolute Aqueous Solvation Free Energy of the Proton journal August 2006
Absolute Potential of the Standard Hydrogen Electrode and the Problem of Interconversion of Potentials in Different Solvents journal June 2010
Systematic Investigation of the Catalytic Cycle of a Single Site Ruthenium Oxygen Evolving Complex Using Density Functional Theory journal July 2011
Reduction of Systematic Uncertainty in DFT Redox Potentials of Transition-Metal Complexes journal March 2012
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
  • Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
  • The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396 https://doi.org/10.1021/jp810292n
journal May 2009
The Proton's Absolute Aqueous Enthalpy and Gibbs Free Energy of Solvation from Cluster-Ion Solvation Data journal October 1998
A soluble copper–bipyridine water-oxidation electrocatalyst journal May 2012
Computational electrochemistry: prediction of liquid-phase reduction potentials journal January 2014
Iridium-based complexes for water oxidation journal January 2015
Electrocatalytic water oxidation by a macrocyclic Cu( ii ) complex in neutral phosphate buffer journal January 2016
Electrocatalytic water oxidation by copper( ii ) complexes containing a tetra- or pentadentate amine-pyridine ligand journal January 2017
Electrocatalytic water oxidation by Cu( ii ) ions in a neutral borate buffer solution journal January 2017
How to make an efficient and robust molecular catalyst for water oxidation journal January 2017
Molecular mechanism of lytic polysaccharide monooxygenases journal January 2018
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy journal January 2005
Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections journal January 2008
Adiabatic time-dependent density functional methods for excited state properties journal October 2002
Gaussian Basis Set for Molecular Wavefunctions Containing Third‐Row Atoms journal February 1970
Self—Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian—Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules journal March 1972
Calculation of Equilibrium Constants for Isotopic Exchange Reactions journal May 1947
Geometries and properties of excited states in the gas phase and in solution: Theory and application of a time-dependent density functional theory polarizable continuum model journal March 2006
A state-specific polarizable continuum model time dependent density functional theory method for excited state calculations in solution journal August 2006
Toward effective and reliable fluorescence energies in solution by a new state specific polarizable continuum model time dependent density functional theory approach journal August 2007
Systematic optimization of long-range corrected hybrid density functionals journal February 2008
Continuous surface charge polarizable continuum models of solvation. I. General formalism journal March 2010
Gaussian basis sets for molecular calculations. The representation of 3 d orbitals in transition‐metal atoms journal May 1977
Self‐consistent molecular orbital methods. XVIII. Constraints and stability in Hartree–Fock theory journal April 1977
Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions journal January 1980
Contracted Gaussian basis sets for molecular calculations. I. Second row atoms, Z=11–18 journal May 1980
Self‐consistent molecular orbital methods 25. Supplementary functions for Gaussian basis sets journal April 1984
On evaluating the reaction path Hamiltonian journal January 1988
Highly correlated systems. Excitation energies of first row transition metals Sc–Cu journal July 1989
Following steepest descent reaction paths. The use of higher energy derivatives with a b i n i t i o electronic structure methods journal October 1990
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
Stability analysis for solutions of the closed shell Kohn–Sham equation journal June 1996
Molecular excitation energies to high-lying bound states from time-dependent density-functional response theory: Characterization and correction of the time-dependent local density approximation ionization threshold journal March 1998
An efficient implementation of time-dependent density-functional theory for the calculation of excitation energies of large molecules journal November 1998
Assessing the accuracy of some popular DFT methods for computing harmonic vibrational frequencies of water clusters journal December 2015
Nucleophilic water attack is not a possible mechanism for O–O bond formation in photosystem II journal April 2017

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
catalysis
chemistry
copper
density functional theory
electrocatalysis
water oxidation
water-nucleophilic attack