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Molecular Electrocatalysts for Oxidation of Hydrogen Using Earth-Abundant Metals: Shoving Protons Around with Proton Relays

Journal Article · · Accounts of Chemical Research
Sustainable, carbon-neutral energy is needed to supplant the worldwide reliance on fossil fuels, to address the persistent problem of increasing emissions of CO2. Solar and wind energy are intermittent, highlighting the need to develop energy storage on a huge scale. Electrocatalysts provide a way to convert between electrical energy generated by renewable energy sources and chemical energy in the form of chemical bonds. Here, the oxidation of hydrogen to give two electrons and two protons is carried out in fuel cells, but the typical catalyst is platinum, a precious metal of low earth-abundance and high cost. In nature, hydrogenases based on iron or iron/nickel reversibly oxidize hydrogen with remarkable efficiency and rates. Functional models of these enzymes are synthesized with the goal of achieving electrocatalytic H2 oxidation using inexpensive, earth-abundant metals along with a key feature identified in the [FeFe]-hydrogenase: an amine base positioned near the metal. The diphosphine ligands PR2NR'2 (1,5-diaza-3,7-diphosphacyclooctane with alkyl or aryl groups on the P and N) are used as ligands in Ni, Fe and Mn complexes. The pendant amines promote binding and heterolytic cleavage of H2, placing the hydride on the metal and the proton on the amine. The pendant amines also serve as proton relays, accelerating intramolecular and intermolecular proton transfers. Electrochemical oxidations and deprotonations by an exogeneous amine base lead to catalytic cycles for oxidation of H2 (1 atm) at room temperature for catalysts derived from [Ni(PCy2NR'2)2]2+, CpC6F5Fe(PtBu2NBn2)H and MnH(PPh2NBn2)(bppm)(CO) [bppm = (PArF2)2CH2)]. The Mn cation [Mn(PPh2NBn2)(bppm)(CO)]+ mediates the rapid (>104 s-1 at -95 °C), reversible heterolytic cleavage of H2. Obtaining the optimal benefit of pendant amines incorporated into the ligand requires that the pendant amine be properly positioned to interact with a M-H or M(H2) bond. In addition, ligands are ideally selected such that the hydride acceptor ability of the metal and the basicity of a pendant are tuned to give low barriers for heterolytic cleavage of the H-H bond and for subsequent proton transfer reactions. Using these principles allows the rational design of electrocatalysts for H2 oxidation using earth-abundant metals.
Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
1582563
Report Number(s):
PNNL-SA--108095
Journal Information:
Accounts of Chemical Research, Journal Name: Accounts of Chemical Research Journal Issue: 7 Vol. 48; ISSN 0001-4842
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Gas reactions under intrapore condensation regime within tailored metal–organic framework catalysts journal May 2019
Noncovalent Immobilization of Molecular Electrocatalysts for Chemical Synthesis: Efficient Electrochemical Alcohol Oxidation with a Pyrene-TEMPO Conjugate journal June 2017
Photochemically Driven Reverse Water-Gas Shift at Ambient Conditions mediated by a Nickel Pincer Complex journal July 2018
H 2 Oxidation Electrocatalysis Enabled by Metal-to-Metal Hydrogen Atom Transfer: A Homolytic Approach to a Heterolytic Reaction journal September 2018
Noncovalent Immobilization of Molecular Electrocatalysts for Chemical Synthesis: Efficient Electrochemical Alcohol Oxidation with a Pyrene-TEMPO Conjugate journal June 2017
Photochemically Driven Reverse Water-Gas Shift at Ambient Conditions mediated by a Nickel Pincer Complex journal July 2018
H 2 Oxidation Electrocatalysis Enabled by Metal-to-Metal Hydrogen Atom Transfer: A Homolytic Approach to a Heterolytic Reaction journal September 2018
Catalyst Pendent-Base Effects on Cyclization of Alkynyl Amines journal July 2018
Electrocatalytic H 2 Evolution by the Co‐Mabiq Complex Requires Tempering of the Redox‐Active Ligand journal June 2019
Facile P−C/C−H Bond-Cleavage Reactivity of Nickel Bis(diphosphine) Complexes journal June 2016
Catalytic Activity of Thiolate-Bridged Diruthenium Complexes Bearing Pendent Ether Moieties in the Oxidation of Molecular Dihydrogen journal December 2016
Z−H Bond Activation in (Di)hydrogen Bonding as a Way to Proton/Hydride Transfer and H 2 Evolution journal December 2017
Manganese Complexes: Hydrogen Generation and Oxidation: Manganese Complexes: Hydrogen Generation and Oxidation journal November 2019
Dinuclear Manganese Carbonyl Complexes: Electrocatalytic Reduction of Protons to Dihydrogen journal February 2019
First-row transition metal complexes of ENENES ligands: the ability of the thioether donor to impact the coordination chemistry journal January 2016
Catalytic cyclization and competitive deactivation with Ru(P R 2 N R′ 2 ) complexes journal January 2016
A macrocyclic ‘Co 0 ’ complex: the relevance of ligand non-innocence to reactivity journal January 2017
Anion control of tautomeric equilibria: Fe–H vs. N–H influenced by NH⋯F hydrogen bonding journal January 2019
Evaluation of attractive interactions in the second coordination sphere of iron complexes containing pendant amines journal January 2019
Optimizing ligand structure for low-loading and fast catalysis for alkynyl-alcohol and -amine cyclization journal January 2019
Thermodynamic and kinetic studies of H 2 and N 2 binding to bimetallic nickel-group 13 complexes and neutron structure of a Ni(η 2 -H 2 ) adduct journal January 2019
Syntheses, crystal structures, and electrochemical studies of dinuclear coordination compounds with the Fe 2 (CO) 6 core journal October 2016
On the concept of frustrated Lewis pairs
  • Fontaine, Frédéric-Georges; Stephan, Douglas W.
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 375, Issue 2101 https://doi.org/10.1098/rsta.2017.0004
journal July 2017
The broadening reach of frustrated Lewis pair chemistry journal December 2016

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