Toward Molecular Catalysts by Computer
Abstract
Rational design of molecular catalysts requires a systematic approach to designing ligands with specific functionality and precisely tailored electronic and steric properties. It then becomes possible to devise computer protocols to design catalysts by computer. In this Account, we first review how thermodynamic properties such as redox potentials (E°), acidity constants (pKa), and hydride donor abilities (ΔGH–) form the basis for a framework for the systematic design of molecular catalysts for reactions that are critical for a secure energy future. Next, we illustrate this for hydrogen evolution and oxidation, oxygen reduction, and CO conversion, and we give references to other instances where it has been successfully applied. The framework is amenable to quantum-chemical calculations and conducive to predictions by computer. We review how density functional theory allows the determination and prediction of these thermodynamic properties within an accuracy relevant to experimentalists (~0.06 eV for redox potentials, ~1 pKa unit for pKa values, and 1–2 kcal/mol for hydricities). Computation yielded correlations among thermodynamic properties as they reflect the electron population in the d shell of the metal center, thus substantiating empirical correlations used by experimentalists. These correlations point to the key role of redox potentials and other properties (pKa of themore »
- Authors:
-
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME)
- Publication Date:
- Research Org.:
- Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL); Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER)
- OSTI Identifier:
- 1773353
- Report Number(s):
- PNNL-SA-105457
Journal ID: ISSN 0001-4842
- Grant/Contract Number:
- AC05-76RL01830
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Accounts of Chemical Research
- Additional Journal Information:
- Journal Volume: 48; Journal Issue: 2; Journal ID: ISSN 0001-4842
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; molecular electrocatalysis; thermodynamics; acidity; redox potentials; density functional theory; hydrogen oxidation and production; oxygen reduction; nitrogen reduction; carbon dioxide reduction; catalyst optimization; computer-aided design
Citation Formats
Raugei, Simone, DuBois, Daniel L., Rousseau, Roger J., Chen, Shentan, Ho, Ming-Hsun, Bullock, Ronald Morris, and Dupuis, Michel. Toward Molecular Catalysts by Computer. United States: N. p., 2015.
Web. doi:10.1021/ar500342g.
Raugei, Simone, DuBois, Daniel L., Rousseau, Roger J., Chen, Shentan, Ho, Ming-Hsun, Bullock, Ronald Morris, & Dupuis, Michel. Toward Molecular Catalysts by Computer. United States. https://doi.org/10.1021/ar500342g
Raugei, Simone, DuBois, Daniel L., Rousseau, Roger J., Chen, Shentan, Ho, Ming-Hsun, Bullock, Ronald Morris, and Dupuis, Michel. Fri .
"Toward Molecular Catalysts by Computer". United States. https://doi.org/10.1021/ar500342g. https://www.osti.gov/servlets/purl/1773353.
@article{osti_1773353,
title = {Toward Molecular Catalysts by Computer},
author = {Raugei, Simone and DuBois, Daniel L. and Rousseau, Roger J. and Chen, Shentan and Ho, Ming-Hsun and Bullock, Ronald Morris and Dupuis, Michel},
abstractNote = {Rational design of molecular catalysts requires a systematic approach to designing ligands with specific functionality and precisely tailored electronic and steric properties. It then becomes possible to devise computer protocols to design catalysts by computer. In this Account, we first review how thermodynamic properties such as redox potentials (E°), acidity constants (pKa), and hydride donor abilities (ΔGH–) form the basis for a framework for the systematic design of molecular catalysts for reactions that are critical for a secure energy future. Next, we illustrate this for hydrogen evolution and oxidation, oxygen reduction, and CO conversion, and we give references to other instances where it has been successfully applied. The framework is amenable to quantum-chemical calculations and conducive to predictions by computer. We review how density functional theory allows the determination and prediction of these thermodynamic properties within an accuracy relevant to experimentalists (~0.06 eV for redox potentials, ~1 pKa unit for pKa values, and 1–2 kcal/mol for hydricities). Computation yielded correlations among thermodynamic properties as they reflect the electron population in the d shell of the metal center, thus substantiating empirical correlations used by experimentalists. These correlations point to the key role of redox potentials and other properties (pKa of the parent aminium for the proton-relay-based catalysts designed in our laboratory) that are easily accessible experimentally or computationally in reducing the parameter space for design. These properties suffice to fully determine free energies maps and profiles associated with catalytic cycles, i.e., the relative energies of intermediates. Their prediction puts us in a position to distinguish a priori between desirable and undesirable pathways and mechanisms. Efficient catalysts have flat free energy profiles that avoid high activation barriers due to low- and high-energy intermediates. The criterion of a flat energy profile can be mathematically resolved in a functional in the reduced parameter space that can be efficaciously calculated by means of the correlation expressions. Optimization of the functional permits the prediction by computer of design points for optimum catalysts. Specifically, the optimization yields the values of the thermodynamic properties for efficient (high rate and low overpotential) catalysts. We are on the verge of design of molecular electrocatalysts by computer. Future efforts must focus on identifying actual ligands that possess these properties. We believe that this can also be achieved through computation, using Taft-like relationships linking molecular composition and structure with electron-donating ability and steric effects. We note also that the approach adopted here of using free energy maps to decipher catalytic pathways and mechanisms does not account for kinetic barriers associated with elementary steps along the catalytic pathway, which may make thermodynamically accessible intermediates kinetically inaccessible. Such an extension of the approach will require further computations that, however, can take advantage of Polanyi-like linear free energy relationships linking activation barriers and reaction free energies.},
doi = {10.1021/ar500342g},
journal = {Accounts of Chemical Research},
number = 2,
volume = 48,
place = {United States},
year = {Fri Jan 09 00:00:00 EST 2015},
month = {Fri Jan 09 00:00:00 EST 2015}
}
Web of Science
Works referenced in this record:
Thermochemistry of Proton-Coupled Electron Transfer Reagents and its Implications
journal, December 2010
- Warren, Jeffrey J.; Tronic, Tristan A.; Mayer, James M.
- Chemical Reviews, Vol. 110, Issue 12
Metal−Hydrogen Bond Dissociation Enthalpies in Series of Complexes of Eight Different Transition Metals †
journal, January 1996
- Wang, Dongmei; Angelici, Robert J.
- Journal of the American Chemical Society, Vol. 118, Issue 5
Gaussian‐1 theory: A general procedure for prediction of molecular energies
journal, May 1989
- Pople, John A.; Head‐Gordon, Martin; Fox, Douglas J.
- The Journal of Chemical Physics, Vol. 90, Issue 10
Relationship between the bite size of diphosphine ligands and tetrahedral distortions of "square-planar" nickel(II) complexes: stabilization of nickel(I) and palladium(I) complexes using diphosphine ligands with large bites
journal, February 1991
- Miedaner, Alex.; Haltiwanger, R. Curtis.; DuBois, Daniel L.
- Inorganic Chemistry, Vol. 30, Issue 3
Powering the planet: Chemical challenges in solar energy utilization
journal, October 2006
- Lewis, N. S.; Nocera, D. G.
- Proceedings of the National Academy of Sciences, Vol. 103, Issue 43, p. 15729-15735
Uncertainty quantification in thermochemistry, benchmarking electronic structure computations, and Active Thermochemical Tables
journal, January 2014
- Ruscic, Branko
- International Journal of Quantum Chemistry, Vol. 114, Issue 17
Thermochemical Insight into the Reduction of CO to CH 3 OH with [Re(CO)] + and [Mn(CO)] + Complexes
journal, June 2014
- Wiedner, Eric S.; Appel, Aaron M.
- Journal of the American Chemical Society, Vol. 136, Issue 24
Comprehensive Thermodynamics of Nickel Hydride Bis(Diphosphine) Complexes: A Predictive Model through Computations
journal, November 2011
- Chen, Shentan; Rousseau, Roger; Raugei, Simone
- Organometallics, Vol. 30, Issue 22
Computing Free Energy Landscapes: Application to Ni-based Electrocatalysts with Pendant Amines for H 2 Production and Oxidation
journal, December 2013
- Chen, Shentan; Ho, Ming-Hsun; Bullock, R. Morris
- ACS Catalysis, Vol. 4, Issue 1
Determining the Overpotential for a Molecular Electrocatalyst
journal, December 2013
- Appel, Aaron M.; Helm, Monte L.
- ACS Catalysis, Vol. 4, Issue 2
Studies of a Series of [Ni(P R 2 N Ph 2 ) 2 (CH 3 CN)] 2+ Complexes as Electrocatalysts for H 2 Production: Substituent Variation at the Phosphorus Atom of the P 2 N 2 Ligand
journal, November 2011
- Kilgore, Uriah J.; Stewart, Michael P.; Helm, Monte L.
- Inorganic Chemistry, Vol. 50, Issue 21
Water electrolysis and photoelectrolysis on electrodes engineered using biological and bio-inspired molecular systems
journal, January 2010
- Tran, Phong D.; Artero, Vincent; Fontecave, Marc
- Energy & Environmental Science, Vol. 3, Issue 6
Chemical accuracy in ab initio thermochemistry and spectroscopy: current strategies and future challenges
journal, January 2012
- Peterson, Kirk A.; Feller, David; Dixon, David A.
- Theoretical Chemistry Accounts, Vol. 131, Issue 1
Electrode potentials and the thermodynamics of isodesmic reactions
journal, September 1991
- Parker, Vernon D.; Handoo, Kishan L.; Roness, Frode
- Journal of the American Chemical Society, Vol. 113, Issue 20
Electrocatalytic Oxygen Reduction by Iron Tetra-arylporphyrins Bearing Pendant Proton Relays
journal, March 2012
- Carver, Colin T.; Matson, Benjamin D.; Mayer, James M.
- Journal of the American Chemical Society, Vol. 134, Issue 12
Molecular Electrocatalysts for the Oxidation of Hydrogen and the Production of Hydrogen - The Role of Pendant Amines as Proton Relays
journal, January 2011
- DuBois, Daniel L.; Bullock, R. Morris
- European Journal of Inorganic Chemistry, Vol. 2011, Issue 7
Distant protonated pyridine groups in water-soluble iron porphyrin electrocatalysts promote selective oxygen reduction to water
journal, January 2012
- Matson, Benjamin D.; Carver, Colin T.; Von Ruden, Amber
- Chemical Communications, Vol. 48, Issue 90
The roles of the first and second coordination spheres in the design of molecular catalysts for H 2 production and oxidation
journal, January 2009
- Rakowski DuBois, M.; DuBois, Daniel L.
- Chem. Soc. Rev., Vol. 38, Issue 1
Proton-Coupled Electron Transfer in Molecular Electrocatalysis: Theoretical Methods and Design Principles
journal, April 2014
- Solis, Brian H.; Hammes-Schiffer, Sharon
- Inorganic Chemistry, Vol. 53, Issue 13
[Ni(P Ph 2 N C6H4X 2 ) 2 ] 2+ Complexes as Electrocatalysts for H 2 Production: Effect of Substituents, Acids, and Water on Catalytic Rates
journal, April 2011
- Kilgore, Uriah J.; Roberts, John A. S.; Pool, Douglas H.
- Journal of the American Chemical Society, Vol. 133, Issue 15
Moving Protons with Pendant Amines: Proton Mobility in a Nickel Catalyst for Oxidation of Hydrogen
journal, September 2011
- O’Hagan, Molly; Shaw, Wendy J.; Raugei, Simone
- Journal of the American Chemical Society, Vol. 133, Issue 36, p. 14301-14312
Synthesis and Hydride Transfer Reactions of Cobalt and Nickel Hydride Complexes to BX 3 Compounds
journal, December 2011
- Mock, Michael T.; Potter, Robert G.; O’Hagan, Molly J.
- Inorganic Chemistry, Vol. 50, Issue 23
Bond energies in solution from electrode potentials and thermochemical cycles. A simplified and general approach
journal, May 1993
- Wayner, Danial D. M.; Parker, Vernon D.
- Accounts of Chemical Research, Vol. 26, Issue 5
Direct Determination of Equilibrium Potentials for Hydrogen Oxidation/Production by Open Circuit Potential Measurements in Acetonitrile
journal, June 2012
- Roberts, John A. S.; Bullock, R. Morris
- Inorganic Chemistry, Vol. 52, Issue 7
Molecular orbital theory of the electronic structure of organic compounds. V. Molecular theory of bond separation
journal, August 1970
- Hehre, Warren J.; Ditchfield, R.; Radom, L.
- Journal of the American Chemical Society, Vol. 92, Issue 16
Ab Initio Calculations of Thermodynamic Hydricities of Transition-Metal Hydrides in Acetonitrile
journal, August 2007
- Qi, Xiu-Juan; Fu, Yao; Liu, Lei
- Organometallics, Vol. 26, Issue 17
Linear Free Energy Relationships from Rates of Esterification and Hydrolysis of Aliphatic and Ortho-substituted Benzoate Esters
journal, June 1952
- Taft, Robert W.
- Journal of the American Chemical Society, Vol. 74, Issue 11
Transition metal-hydrogen and metal-carbon bond strengths: the keys to catalysis
journal, June 1990
- Simoes, J. A. Martinho; Beauchamp, J. L.
- Chemical Reviews, Vol. 90, Issue 4
Thermodynamic Studies and Hydride Transfer Reactions from a Rhodium Complex to BX 3 Compounds
journal, October 2009
- Mock, Michael T.; Potter, Robert G.; Camaioni, Donald M.
- Journal of the American Chemical Society, Vol. 131, Issue 40
Solar Energy Supply and Storage for the Legacy and Nonlegacy Worlds
journal, November 2010
- Cook, Timothy R.; Dogutan, Dilek K.; Reece, Steven Y.
- Chemical Reviews, Vol. 110, Issue 11
Free-Energy Relationships between the Proton and Hydride Donor Abilities of [HNi(diphosphine) 2 ] + Complexes and the Half-Wave Potentials of Their Conjugate Bases
journal, April 2001
- Berning, Douglas E.; Miedaner, Alex; Curtis, Calvin J.
- Organometallics, Vol. 20, Issue 9
Proton-Coupled Electron Transfer in Solution, Proteins, and Electrochemistry †
journal, November 2008
- Hammes-Schiffer, Sharon; Soudackov, Alexander V.
- The Journal of Physical Chemistry B, Vol. 112, Issue 45
Proton Delivery and Removal in [Ni(P R 2 N R ′ 2 ) 2 ] 2+ Hydrogen Production and Oxidation Catalysts
journal, November 2012
- O’Hagan, Molly; Ho, Ming-Hsun; Yang, Jenny Y.
- Journal of the American Chemical Society, Vol. 134, Issue 47
The Role of Pendant Amines in the Breaking and Forming of Molecular Hydrogen Catalyzed by Nickel Complexes
journal, April 2012
- Raugei, Simone; Chen, Shentan; Ho, Ming-Hsun
- Chemistry - A European Journal, Vol. 18, Issue 21
Hydride Transfer from Rhodium Complexes to Triethylborane
journal, August 2006
- DuBois, Daniel L.; Blake, Daniel M.; Miedaner, Alex
- Organometallics, Vol. 25, Issue 18
Ab Initio Calculations of p K a Values of Transition-Metal Hydrides in Acetonitrile
journal, December 2006
- Qi, Xiu-Juan; Liu, Lei; Fu, Yao
- Organometallics, Vol. 25, Issue 25
Development of Molecular Electrocatalysts for Energy Storage
journal, February 2014
- DuBois, Daniel L.
- Inorganic Chemistry, Vol. 53, Issue 8
Homogeneous Ni Catalysts for H 2 Oxidation and Production: An Assessment of Theoretical Methods, from Density Functional Theory to Post Hartree−Fock Correlated Wave-Function Theory
journal, December 2010
- Chen, Shentan; Raugei, Simone; Rousseau, Roger
- The Journal of Physical Chemistry A, Vol. 114, Issue 48
Works referencing / citing this record:
Mapping free energy regimes in electrocatalytic reductions to screen transition metal-based catalysts
journal, January 2019
- Ramakrishnan, Srinivasan; Moretti, Ross A.; Chidsey, Christopher E. D.
- Chemical Science, Vol. 10, Issue 32
A Supramolecular Palladium Catalyst Displaying Substrate Selectivity by Remote Control
journal, December 2018
- Zardi, Paolo; Roisnel, Thierry; Gramage‐Doria, Rafael
- Chemistry – A European Journal
Homogenous Meets Heterogenous and Electro‐Catalysis: Iron‐Nitrogen Molecular Complexes within Carbon Materials for Catalytic Applications
journal, June 2019
- Li, Alain; Nicolae, Sabina A.; Qiao, Mo
- ChemCatChem, Vol. 11, Issue 16
Increasing the rate of hydrogen oxidation without increasing the overpotential: a bio-inspired iron molecular electrocatalyst with an outer coordination sphere proton relay
journal, January 2015
- Darmon, Jonathan M.; Kumar, Neeraj; Hulley, Elliott B.
- Chemical Science, Vol. 6, Issue 5
Fast screening of homogeneous catalysis mechanisms using graph-driven searches and approximate quantum chemistry
journal, January 2019
- Robertson, Christopher; Habershon, Scott
- Catalysis Science & Technology, Vol. 9, Issue 22
Thermodynamic Properties of Hydrogen-Producing Cobaloxime Catalysts: A Density Functional Theory Analysis
journal, January 2019
- Chen, Jinfan; Sit, Patrick H. -L.
- ACS Omega, Vol. 4, Issue 1
Increasing the rate of hydrogen oxidation without increasing the overpotential: a bio-inspired iron molecular electrocatalyst with an outer coordination sphere proton relay
journal, January 2015
- Darmon, Jonathan M.; Kumar, Neeraj; Hulley, Elliott B.
- Chemical Science, Vol. 6, Issue 5