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Title: Toward Molecular Catalysts by Computer

Journal Article · · Accounts of Chemical Research, 48(2):248-255
DOI:https://doi.org/10.1021/ar500342g· OSTI ID:1171871
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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 predict accurately the required properties and ultimately to design catalysts by computer. In this account we first review how thermodynamic properties such as oxidation-reduction potentials (E0), acidities (pKa), and hydride donor abilities (ΔGH-) form the basis for a systematic design of molecular catalysts for reactions that are critical for a secure energy future (hydrogen evolution and oxidation, oxygen and nitrogen reduction, and carbon dioxide reduction). We highlight how density functional theory allows us to determine and predict these properties within “chemical” accuracy (~ 0.06 eV for redox potentials, ~ 1 pKa unit for pKa values, and ~ 1.5 kcal/mol for hydricities). These quantities determine free energy maps and profiles associated with catalytic cycles, i.e. the relative energies of intermediates, and help us distinguish between desirable and high-energy pathways and mechanisms. Good catalysts have flat profiles that avoid high activation barriers due to low and high energy intermediates. We illustrate how the criterion of a flat energy profile lends itself to the prediction of design points by computer for optimum catalysts. This research was carried out in the Center for Molecular Electro-catalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory (PNNL) is operated for the DOE by Battelle.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
DOE Contract Number:
AC05-76RL01830
OSTI ID:
1171871
Report Number(s):
PNNL-SA-105457; KC0307010
Journal Information:
Accounts of Chemical Research, 48(2):248-255, Journal Name: Accounts of Chemical Research, 48(2):248-255
Country of Publication:
United States
Language:
English

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Fast screening of homogeneous catalysis mechanisms using graph-driven searches and approximate quantum chemistry journal January 2019
Mapping free energy regimes in electrocatalytic reductions to screen transition metal-based catalysts journal January 2019
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THERMODYNAMICS
PH VALUE
REDOX POTENTIAL
COMPUTER-AIDED DESIGN
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