Using Brønsted-Evans-Polanyi relations to predict electrode potential-dependent activation energies

Akhade, Sneha A.; Nidzyn, Robert M.; Rostamikia, Gholamreza; Janik, Michael J.

doi:10.1016/j.cattod.2018.03.048

Cited by 46 publications

(46 citation statements)

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“…The parameter a was set to a typical value of 0.6, and b was set to a moderate value of 100 kJ mol À1 based on literature of calculated BEP relationships. 39,46,49 Binding energies at each oscillation endpoint were calculated using linear scaling relationships (LSRs) between the surface adsorbates. Previously dened parameters including g i/j and d i-j were used to fully specify the binding energies of B* and C* relative to the binding energy of A.…”

Section: Methodsmentioning

confidence: 99%

Catalytic resonance theory: parallel reaction pathway control

et al. 2020

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Section: Methodsmentioning

confidence: 99%

Catalytic resonance theory: parallel reaction pathway control

et al. 2020

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“…As for the value of the BEP coefficient, β = 0.5 is a frequent assumption, although there is no physical basis for why β should be 0.5 or why it should be independent of the material (Koper, 2011a;Akhade et al, 2018). There is also no basis for why β should be constant throughout the various elementary steps of a multistep electrocatalytic reaction.…”

Section: Validity Of the Bep Relationshipmentioning

confidence: 99%

The Sabatier Principle in Electrocatalysis: Basics, Limitations, and Extensions

2021

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The Sabatier principle, which states that the binding energy between the catalyst and the reactant should be neither too strong nor too weak, has been widely used as the key criterion in designing and screening electrocatalytic materials necessary to promote the sustainability of our society. The widespread success of density functional theory (DFT) has made binding energy calculations a routine practice, turning the Sabatier principle from an empirical principle into a quantitative predictive tool. Given its importance in electrocatalysis, we have attempted to introduce the reader to the fundamental concepts of the Sabatier principle with a highlight on the limitations and challenges in its current thermodynamic context. The Sabatier principle is situated at the heart of catalyst development, and moving beyond its current thermodynamic framework is expected to promote the identification of next-generation electrocatalysts.

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“…In yet another approach 18,19 electrochemical barriers are estimated in a two-step procedure inspired by Markus theory. First, the activation energy of the corresponding non-107 electrochemical reaction is calculated (e.g.…”

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Assessment of Constant-Potential Implicit Solvation Calculations of Electrochemical Energy Barriers for H₂ Evolution on Pt

et al. 2019

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Theoretical estimation of the activation energy 2 of electrochemical reactions is of critical impor-3 tance but remains challenging. In this work, we 4 address the usage of an implicit solvation model 5 for describing hydrogen evolution reaction steps 6 on Pt(111) and Pt(110), and compare with 7 the 'extrapolation' approach as well as single-8 crystal measurements. We find that both meth-9 ods yield qualitatively similar results, which are 10 in fair agreement with the experimental data. 11 Care should be taken, however, in addressing 12 spurious electrostatic interactions between pe-13 riodically repeated slabs in the VASPsol im-14 plementation. Considering the lower computa-15 tional cost and higher flexibility of the implicit 16 solvation approach, we expect this method to 17 become a valuable tool in electrocatalysis. 18 157 tions involving H atoms adsorbed in threefold 158 hollow sites at a coverage of up to 1 ML. Also, 159 the HER steps on (110) facets are included, as experimental Tafel slopes are here easier to an-161 alyze and indicate a Volmer-Tafel mechanism 162 with the Tafel reaction as the rate-determining 163 step (RDS). 35 164 It should be noted that the above considera-457 face. The magnitude of the corresponding pre-458 exponential factor (circa 10 10 mA/cm 2) is char-459 acteristic of a process involving only surface 460 adsorbates, supporting the Tafel reaction as 461 the RDS. These findings therefore qualitatively 462 agree with the computational results described 463 in the previous paragraphs, where the same 464 Tafel RDS is found, though with a somewhat 465 higher activation energy (0.80-0.85 eV). As the 466 barrier for the Tafel step is not sensitive to the 467 water structure at the interface, this does not, 468 unfortunately, allow to discriminate between 469 different types of water models. 470 Comparison with other implicit solvent 471 calculations 472 Fang et al. have previously addressed 31 the 473 HER on Pt(111) using a similar method im-474 plemented in the SIESTA code. 32,33 At 0 V SHE 475 and a hydrogen coverage at or below 1 ML, the 476 Tafel barrier reported by Fang et al. (0.92 eV) 477 agrees well with our calculations, while the re-478 ported Volmer and Heyrovský barrier heights 479 are significantly lower than ours (< 0.2 eV and 480 0.93 eV, respectively). In attempting to locate 481 the origins of this difference for the Volmer re-482 action, we find that the inclusion of zero-point 483 vibrational energy corrections lowers the calcu-484 lated barrier by 0.10 eV, while applying the 485

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Using Brønsted-Evans-Polanyi relations to predict electrode potential-dependent activation energies

Cited by 46 publications

References 59 publications

Catalytic resonance theory: parallel reaction pathway control

Catalytic resonance theory: parallel reaction pathway control

The Sabatier Principle in Electrocatalysis: Basics, Limitations, and Extensions

Assessment of Constant-Potential Implicit Solvation Calculations of Electrochemical Energy Barriers for H₂ Evolution on Pt

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Using Brønsted-Evans-Polanyi relations to predict electrode potential-dependent activation energies

Cited by 46 publications

References 59 publications

Catalytic resonance theory: parallel reaction pathway control

Catalytic resonance theory: parallel reaction pathway control

The Sabatier Principle in Electrocatalysis: Basics, Limitations, and Extensions

Assessment of Constant-Potential Implicit Solvation Calculations of Electrochemical Energy Barriers for H2 Evolution on Pt

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Assessment of Constant-Potential Implicit Solvation Calculations of Electrochemical Energy Barriers for H₂ Evolution on Pt