A simple method to approximate electrode potential-dependent activation energies using density functional theory

Akhade, Sneha A.; Bernstein, Nicole J.; Esopi, Monica R.; Regula, Michael; Janik, Michael J.

doi:10.1016/j.cattod.2017.01.050

Cited by 99 publications

(110 citation statements)

References 53 publications

Supporting

Mentioning

107

Contrasting

Order By: Relevance

“…The potential effect on thermodynamic reaction free energy was considered by changing the chemical potential of (H + + e − ) by -eU, as suggested in the computational hydrogen electrode 47 approximation. The potential-dependent kinetic barriers of electrochemical reaction (*A + H + + e − → *AH) were calculated by using an equivalent analogous non-electrochemical reaction (*A + *H → *AH) combined with Marcus theory, an effective method developed by Janik et al 49,50 .…”

Section: Methodsmentioning

confidence: 99%

Unveiling hydrocerussite as an electrochemically stable active phase for efficient carbon dioxide electroreduction to formate

et al. 2020

View full text Add to dashboard Cite

For most metal-containing CO 2 reduction reaction (CO 2 RR) electrocatalysts, the unavoidable self-reduction to zero-valence metal will promote hydrogen evolution, hence lowering the CO 2 RR selectivity. Thus it is challenging to design a stable phase with resistance to electrochemical self-reduction as well as high CO 2 RR activity. Herein, we report a scenario to develop hydrocerussite as a stable and active electrocatalyst via in situ conversion of a complex precursor, tannin-lead(II) (TA-Pb) complex. A comprehensive characterization reveals the in situ transformation of TA-Pb to cerussite (PbCO 3), and sequentially to hydrocerussite (Pb 3 (CO 3) 2 (OH) 2), which finally serves as a stable and active phase under CO 2 RR condition. Both experiments and theoretical calculations confirm the high activity and selectivity over hydrocerussite. This work not only offers a new approach of enhancing the selectivity in CO 2 RR by suppressing the self-reduction of electrode materials, but also provides a strategy for studying the reaction mechanism and active phases of electrocatalysts.

show abstract

Section: Methodsmentioning

confidence: 99%

Unveiling hydrocerussite as an electrochemically stable active phase for efficient carbon dioxide electroreduction to formate

et al. 2020

View full text Add to dashboard Cite

show abstract

“…Activation energies were calculated for a product state that involved adsorbed hydroxide (non-electrochemical) or solution-phase hydroxide (electrochemical, the alkaline Volmer step). The activation energies for dissociation to solution-phase hydroxide were calculated by taking the barrier for the reaction to the adsorbed hydroxide as the potential-dependent barrier for the reaction to solution-phase hydroxide at the potential at which the solution-phase hydroxide and the adsorbed hydroxide are in equilibrium 28 . These barriers were taken to be the same for metals that have an adsorption potential of hydroxide below 0 V RHE (Re, Ru and Rh), as hydroxide adsorption is favourable on these metals at the equilibrium potential for hydrogen evolution (0 V RHE ).…”

Section: Her Activitymentioning

confidence: 99%

“…Potential dependent activation energy. Potential dependent activation energies for water dissociation into solution-phase hydroxide (electrochemical) were calculated by taking the barrier calculated by the TS search for water dissociation to adsorbed hydroxide (chemical) as the barrier for the electrochemical dissociation at the potential where the FS (adsorbed hydroxide, OH* + 2H 2 O* + Na* + H*) was in equilibrium with solution-phase hydroxide 28 . The potential at which the FS is in equilibrium with the solution-phase hydroxide was calculated following reaction (15) (with reference to adsorbed water, instead of to solution-phase hydroxide explicitly, as done for the OH* adsorption energy in equation ( 11)), using equation (11) but solving for the potential that gives a free energy change of adsorption of 0.…”

Section: Computational Details-thermodynamics and Kinetics Oh* Adsorption Energymentioning

confidence: 99%

The role of adsorbed hydroxide in hydrogen evolution reaction kinetics on modified platinum

2020

View full text Add to dashboard Cite

“…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.…”

mentioning

confidence: 99%

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

et al. 2019

View full text Add to dashboard Cite

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

show abstract

A simple method to approximate electrode potential-dependent activation energies using density functional theory

Cited by 99 publications

References 53 publications

Unveiling hydrocerussite as an electrochemically stable active phase for efficient carbon dioxide electroreduction to formate

Unveiling hydrocerussite as an electrochemically stable active phase for efficient carbon dioxide electroreduction to formate

The role of adsorbed hydroxide in hydrogen evolution reaction kinetics on modified platinum

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

Contact Info

Product

Resources

About

A simple method to approximate electrode potential-dependent activation energies using density functional theory

Cited by 99 publications

References 53 publications

Unveiling hydrocerussite as an electrochemically stable active phase for efficient carbon dioxide electroreduction to formate

Unveiling hydrocerussite as an electrochemically stable active phase for efficient carbon dioxide electroreduction to formate

The role of adsorbed hydroxide in hydrogen evolution reaction kinetics on modified platinum

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

Contact Info

Product

Resources

About

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