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Title: Immobilization of an Amphiphilic Molecular Cobalt Catalyst on Carbon Black for Ligand-Assisted Water Oxidation

Journal Article · · Inorganic Chemistry
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  1. Wayne State Univ., Detroit, MI (United States)
  2. Argonne National Lab. (ANL), Lemont, IL (United States)
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We have prepared the amphiphilic molecular catalyst [CoIII(LOC18)(pyrr)2]ClO4, where LOC18 is the deprotonated form of N,N'-[4,5-bis(octadecyloxy)-1,2- phenylene]dipicolinamide. Species can be anchored onto a carbon black support to yield the assembly 1@CB, which can catalyze water oxidation at an affordable onset overpotential of 0.32 V, with a current density of 10 mA/cm2 at 0.37 V. Furthermore, 1@CB displays TOF = 3850 h–1. A mechanism is proposed based on the experimental and density-functionaltheory- calculated data.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1476901
Journal Information:
Inorganic Chemistry, Vol. 57, Issue 16; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 15 works
Citation information provided by
Web of Science

References (57)

Redox Non-innocent Ligand Controls Water Oxidation Overpotential in a New Family of Mononuclear Cu-Based Efficient Catalysts journal May 2015
Improving Singlet Oxygen Resistance during Photochemical Water Oxidation by Cobalt Porphyrin Catalysts journal March 2015
Redox Non-Innocent Ligands: Versatile New Tools to Control Catalytic Reactions journal January 2012
Noncovalent Immobilization of a Pyrene-Modified Cobalt Corrole on Carbon Supports for Enhanced Electrocatalytic Oxygen Reduction and Oxygen Evolution in Aqueous Solutions journal August 2016
Highly Efficient Oxidation of Water by a Molecular Catalyst Immobilized on Carbon Nanotubes journal October 2011
Immobilization of a molecular catalyst on carbon nanotubes for highly efficient electro-catalytic water oxidation journal January 2014
Efficient water oxidation with electromodified Langmuir–Blodgett films of procatalytic [Co III (N 2 O 3 )] metallosurfactants on electrodes journal January 2016
Efficient Water Oxidation Using CoMnP Nanoparticles journal March 2016
Boosting the Catalytic Performance of Iron Phosphide Nanorods for the Oxygen Evolution Reaction by Incorporation of Manganese journal March 2017
Synthesis and oxygen evolution reaction (OER) catalytic performance of Ni 2−x Ru x P nanocrystals: enhancing activity by dilution of the noble metal journal January 2017
Rectification in Nanoscale Devices Based on an Asymmetric Five-Coordinate Iron(III) Phenolate Complex journal October 2013
The Mechanisms of Rectification in Au|Molecule|Au Devices Based on Langmuir-Blodgett Monolayers of Iron(III) and Copper(II) Surfactants journal November 2014
Langmuir–Blodgett films of salophen-based metallosurfactants as surface pretreatment coatings for corrosion mitigation journal January 2016
Confirmation of the Rectifying Behavior in a Pentacoordinate [N 2 O 2 ] Iron(III) Surfactant Using a “Eutectic GaIn | LB Monolayer | Au” Assembly journal May 2016
Synthesis of novel bis(amides) by means of triphenyl phosphite intermediates journal October 1978
Synthesis and characterization of trans-[Co(III)(bpb)(amine)2]X (X=NCS, ClO4). X-ray crystal structure of trans-[Co(III)(bpb)(pyrrolidine)2]NCS·0.5H2O containing intermolecular NH⋯OC hydrogen-bonding journal October 2002
Synthesis, structure, and electrochemistry of pyridinecarboxamide cobalt(III) complexes; the effect of bridge substituents on the redox properties journal September 2008
Ferrocene as an internal standard for electrochemical measurements journal September 1980
1,2-Bis(pyridine-2-carboxamido)benzenate(2−), (bpb) 2- :  A Noninnocent Ligand. Syntheses, Structures, and Mechanisms of Formation of [( n -Bu) 4 N][Fe IV 2 (μ-N)(bpb) 2 (X) 2 ] (X = CN - , N 3 - ) and the Electronic Structures of [M III (bpb ox1 )(CN) 2 ] (M = Co, Fe) journal July 2000
Dinuclear Cyano Complexes of Cobalt(III) and Iron(III) Containing Noninnocent 1,2,4,5-Tetrakis(2-pyridinecarboxamido)benzene Bridging Ligands journal February 2003
Deactivation of a Cobalt Catalyst for Water Reduction through Valence Tautomerism journal May 2017
Selective propane dehydrogenation with single-site CoII on SiO2 by a non-redox mechanism journal February 2015
The Hydrogen Catalyst Cobaloxime: A Multifrequency EPR and DFT Study of Cobaloxime’s Electronic Structure journal February 2012
Evaluation of the coordination preferences and catalytic pathways of heteroaxial cobalt oximes towards hydrogen generation journal January 2016
A Tailor-Made Molecular Ruthenium Catalyst for the Oxidation of Water and Its Deactivation through Poisoning by Carbon Monoxide journal March 2013
Biomimetic Hydrocarbon Oxidation Catalyzed by Nonheme Iron(III) Complexes with Peracids: Evidence for an FeVO Species journal November 2007
Amide-Based Nonheme Cobalt(III) Olefin Epoxidation Catalyst: Partition of Multiple Active Oxidants CoVO, CoIVO, and CoIIIOO(O)CR journal March 2012
Robust and Efficient Amide‐Based Nonheme Manganese(III) Hydrocarbon Oxidation Catalysts: Substrate and Solvent Effects on Involvement and Partition of Multiple Active Oxidants journal May 2011
Benchmarking Heterogeneous Electrocatalysts for the Oxygen Evolution Reaction journal October 2013
Water Oxidation at Electrodes Modified with Earth-Abundant Transition-Metal Catalysts journal October 2014
Electrocatalytic oxygen evolution reaction for energy conversion and storage: A comprehensive review journal July 2017
Electrocatalysis for the oxygen evolution reaction: recent development and future perspectives journal January 2017
Ligand Modification Transforms a Catalase Mimic into a Water Oxidation Catalyst journal July 2014
Cobalt porphyrins as homogeneous catalysts for water oxidation journal January 2013
Homogeneous Photocatalytic Water Oxidation with a Dinuclear Co III –Pyridylmethylamine Complex journal January 2016
Progress in Base-Metal Water Oxidation Catalysis journal July 2014
Efficient Electrochemical and Photoelectrochemical H 2 Production from Water by a Cobalt Dithiolene One-Dimensional Metal–Organic Surface journal October 2015
Computational electrochemistry: prediction of liquid-phase reduction potentials journal January 2014
Homogeneous Photochemical Water Oxidation by Biuret-Modified Fe-TAML: Evidence of Fe V (O) Intermediate journal August 2014
Electrocatalytic water oxidation by a molecular cobalt complex through a high valent cobalt oxo intermediate journal January 2016
A Structurally Characterized Nonheme Cobalt–Hydroperoxo Complex Derived from Its Superoxo Intermediate via Hydrogen Atom Abstraction journal October 2016
Synthesis and reactivity of a mononuclear non-haem cobalt(IV)-oxo complex journal March 2017
An Oxocobalt(IV) Complex Stabilized by Lewis Acid Interactions with Scandium(III) Ions journal December 2010
Reaction Mechanism of Water Oxidation Catalyzed by Iron Tetraamido Macrocyclic Ligand Complexes - A DFT Study: Water Oxidation Catalyzed by Iron Complexes journal September 2013
Reparameterization of hybrid functionals based on energy differences of states of different multiplicity
  • Reiher, Markus; Salomon, Oliver; Artur Hess, Bernd
  • Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), Vol. 107, Issue 1 https://doi.org/10.1007/s00214-001-0300-3
journal December 2001
Energy‐adjusted a b i n i t i o pseudopotentials for the first row transition elements journal January 1987
Self‐consistent molecular orbital methods. XXIII. A polarization‐type basis set for second‐row elements journal October 1982
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
Calculations of p K a ’s and Redox Potentials of Nucleobases with Explicit Waters and Polarizable Continuum Solvation journal October 2014
Theoretical Calculation of p K a ’s of Selenols in Aqueous Solution Using an Implicit Solvation Model and Explicit Water Molecules journal October 2016
Density Functional Theory Calculation of p K a ’s of Thiols in Aqueous Solution Using Explicit Water Molecules and the Polarizable Continuum Model journal June 2016
Improved p K a Prediction of Substituted Alcohols, Phenols, and Hydroperoxides in Aqueous Medium Using Density Functional Theory and a Cluster-Continuum Solvation Model journal June 2017
Thermodynamics of the Electron and the Proton journal June 1994
Comment on “Accurate Experimental Values for the Free Energies of Hydration of H + , OH - , and H 3 O + ” journal December 2005
Absolute Potential of the Standard Hydrogen Electrode and the Problem of Interconversion of Potentials in Different Solvents journal June 2010
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
Solvation thermodynamics of nonionic solutes journal August 1984

Cited By (2)

Recent Advances in the Development of Molecular Catalyst‐Based Anodes for Water Oxidation toward Artificial Photosynthesis journal November 2018
Catalysis of a Single Transition Metal Site for Water Oxidation: From Mononuclear Molecules to Single Atoms journal December 2019

Figures / Tables (6)

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Scheme 1(p. 2)figure Scheme 1
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Water oxidation
cobalt
molecular catalysts
redox-active ligand