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Hydrogen Production and Utilization in a Membrane Reactor
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Diabatic model for electrochemical hydrogen evolution based on constrained DFT configuration interaction.

Nico Holmberg1, Kari Laasonen1

  • 1Department of Chemistry and Materials Science, Aalto University, P.O. Box 16100, 00076 Aalto, Finland.

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|September 17, 2018
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Summary
This summary is machine-generated.

Constrained density functional theory (CDFT) corrects electron delocalization errors in electrocatalysis. This method refines energy profiles for reactions like hydrogen evolution, improving accuracy for kinetic models.

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Area of Science:

  • Computational Chemistry
  • Electrocatalysis
  • Materials Science

Background:

  • Density functional theory (DFT) models for electrocatalysis suffer from inaccuracies due to electron delocalization.
  • These errors affect predictions of reaction and activation energies, limiting model reliability.

Purpose of the Study:

  • To introduce a constrained DFT (CDFT) approach to mitigate overdelocalization errors in electrocatalytic kinetic models.
  • To apply CDFT to the hydrogen evolution reaction (HER) mechanism and assess its impact on energy profiles.

Main Methods:

  • A constrained DFT (CDFT) method was developed and applied a posteriori to reaction path configurations.
  • The approach involves constructing diabatic states with density constraints and performing CDFT-CI calculations.
  • The method was validated and then used to study HER on carbon nanotubes.

Main Results:

  • CDFT-CI calculations showed increased activation energies and decreased reaction energies for HER compared to standard DFT.
  • The refined energy profiles offer a more accurate representation of the catalytic process.
  • The study demonstrates the effectiveness of CDFT in correcting spurious delocalization effects.

Conclusions:

  • The proposed CDFT-CI method effectively addresses overdelocalization in DFT for electrocatalysis.
  • This approach can improve the accuracy of kinetic models for reactions like HER and potentially oxygen reduction reaction.
  • CDFT offers a promising avenue for more reliable computational studies in electrocatalysis.