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Title: Ab Initio-Based Kinetic Modeling for the Design of Molecular Catalysts: The Case of H 2 Production Electrocatalysts

Abstract

Design of fast, efficient electrocatalysts for energy production and energy utilization requires a systematic approach to predict and tune the energetics of reaction intermediates and the kinetic barriers between them as well as to tune reaction conditions (e.g., concentration of reactants, acidity of the reaction medium, and applied electric potential). Thermodynamics schemes based on the knowledge of pKa values, hydride donor ability, redox potentials, and other relevant thermodynamic properties have been demonstrated to be very effective for exploring possible reaction pathways. We seek to identify high-energy intermediates, which may represent a catalytic bottleneck, and low-energy intermediates, which may represent a thermodynamic sink. In this study, working on a well-established Ni-based bioinspired electrocatalyst for H2 production, we performed a detailed kinetic analysis of the catalytic pathways to assess the limitations of our current (standard state) thermodynamic analysis with respect to prediction of optimal catalyst performance. To this end, we developed a microkinetic model based on extensive ab initio simulations. The model was validated against available experimental data, and it reproduces remarkably well the observed turnover rate as a function of the acid concentration and catalytic conditions, providing valuable information on the main factors limiting catalysis. Using this kinetic analysis as amore » reference, we show that indeed a purely thermodynamic analysis of the possible reaction pathways provides us with valuable information, such as a qualitative picture of the species involved during catalysis, identification of the possible branching points, and the origin of the observed overpotential, which are critical insights for electrocatalyst design. However, a significant limitation of this approach is understanding how these insights relate to rate, which is an equally critical piece of information. Taking our analysis a step further, we show that the kinetic model can easily be extended to different catalytic conditions by using linear free energy relationships for activation barriers based on simple thermodynamics quantities, such as pKa values. Finally, we outline a possible procedure to extend it to other catalytic platforms, making it a general and effective way to design catalysts with improved performance.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1]
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  1. Center for Molecular Electrocatalysis, Pacific Northwest National Laboratory, P.O. Box 999, K1-83, Richland, Washington 99352, United States
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1213957
Alternate Identifier(s):
OSTI ID: 1386994
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Published Article
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Name: ACS Catalysis Journal Volume: 5 Journal Issue: 9; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (homogeneous); catalysis (heterogeneous); solar (fuels); bio-inspired; energy storage (including batteries and capacitors); hydrogen and fuel cells; charge transport; materials and chemistry by design; synthesis (novel materials)

Citation Formats

Ho, Ming-Hsun, Rousseau, Roger, Roberts, John A. S., Wiedner, Eric S., Dupuis, Michel, DuBois, Daniel L., Bullock, R. Morris, and Raugei, Simone. Ab Initio-Based Kinetic Modeling for the Design of Molecular Catalysts: The Case of H 2 Production Electrocatalysts. United States: N. p., 2015. Web. doi:10.1021/acscatal.5b01152.
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Ho, Ming-Hsun, Rousseau, Roger, Roberts, John A. S., Wiedner, Eric S., Dupuis, Michel, DuBois, Daniel L., Bullock, R. Morris, & Raugei, Simone. Ab Initio-Based Kinetic Modeling for the Design of Molecular Catalysts: The Case of H 2 Production Electrocatalysts. United States. https://doi.org/10.1021/acscatal.5b01152
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Ho, Ming-Hsun, Rousseau, Roger, Roberts, John A. S., Wiedner, Eric S., Dupuis, Michel, DuBois, Daniel L., Bullock, R. Morris, and Raugei, Simone. Thu . "Ab Initio-Based Kinetic Modeling for the Design of Molecular Catalysts: The Case of H 2 Production Electrocatalysts". United States. https://doi.org/10.1021/acscatal.5b01152.
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@article{osti_1213957,
title = {Ab Initio-Based Kinetic Modeling for the Design of Molecular Catalysts: The Case of H 2 Production Electrocatalysts},
author = {Ho, Ming-Hsun and Rousseau, Roger and Roberts, John A. S. and Wiedner, Eric S. and Dupuis, Michel and DuBois, Daniel L. and Bullock, R. Morris and Raugei, Simone},
abstractNote = {Design of fast, efficient electrocatalysts for energy production and energy utilization requires a systematic approach to predict and tune the energetics of reaction intermediates and the kinetic barriers between them as well as to tune reaction conditions (e.g., concentration of reactants, acidity of the reaction medium, and applied electric potential). Thermodynamics schemes based on the knowledge of pKa values, hydride donor ability, redox potentials, and other relevant thermodynamic properties have been demonstrated to be very effective for exploring possible reaction pathways. We seek to identify high-energy intermediates, which may represent a catalytic bottleneck, and low-energy intermediates, which may represent a thermodynamic sink. In this study, working on a well-established Ni-based bioinspired electrocatalyst for H2 production, we performed a detailed kinetic analysis of the catalytic pathways to assess the limitations of our current (standard state) thermodynamic analysis with respect to prediction of optimal catalyst performance. To this end, we developed a microkinetic model based on extensive ab initio simulations. The model was validated against available experimental data, and it reproduces remarkably well the observed turnover rate as a function of the acid concentration and catalytic conditions, providing valuable information on the main factors limiting catalysis. Using this kinetic analysis as a reference, we show that indeed a purely thermodynamic analysis of the possible reaction pathways provides us with valuable information, such as a qualitative picture of the species involved during catalysis, identification of the possible branching points, and the origin of the observed overpotential, which are critical insights for electrocatalyst design. However, a significant limitation of this approach is understanding how these insights relate to rate, which is an equally critical piece of information. Taking our analysis a step further, we show that the kinetic model can easily be extended to different catalytic conditions by using linear free energy relationships for activation barriers based on simple thermodynamics quantities, such as pKa values. Finally, we outline a possible procedure to extend it to other catalytic platforms, making it a general and effective way to design catalysts with improved performance.},
doi = {10.1021/acscatal.5b01152},
journal = {ACS Catalysis},
number = 9,
volume = 5,
place = {United States},
year = {Thu Aug 27 00:00:00 EDT 2015},
month = {Thu Aug 27 00:00:00 EDT 2015}
}
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  • Theoretica Chimica Acta, Vol. 77, Issue 2
  • DOI: 10.1007/BF01114537

Investigating and Exploiting the Electrocatalytic Properties of Hydrogenases
journal, October 2007

  • Vincent, Kylie A.; Parkin, Alison; Armstrong, Fraser A.
  • Chemical Reviews, Vol. 107, Issue 10, p. 4366-4413
  • DOI: 10.1021/cr050191u

Hydrogen Evolution from Formic Acid in an Ionic Liquid Solvent: A Mechanistic Study by ab Initio Molecular Dynamics
journal, December 2011

  • Bhargava, B. L.; Yasaka, Yoshiro; Klein, Michael L.
  • The Journal of Physical Chemistry B, Vol. 115, Issue 48
  • DOI: 10.1021/jp204007w

Theory of Stationary Electrode Polarography. Single Scan and Cyclic Methods Applied to Reversible, Irreversible, and Kinetic Systems.
journal, April 1964

  • Nicholson, R. S.; Shain, Irving
  • Analytical Chemistry, Vol. 36, Issue 4, p. 706-723
  • DOI: 10.1021/ac60210a007

Escaping free-energy minima
journal, September 2002

  • Laio, A.; Parrinello, M.
  • Proceedings of the National Academy of Sciences, Vol. 99, Issue 20
  • DOI: 10.1073/pnas.202427399

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
  • DOI: 10.1021/jp106800n
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