Modeling the electrified solid–liquid interface

Rossmeisl, Jan; Skúlason, Egill; Björketun, Mårten E.; Tripković, Vladimir; Nørskov, Jens K.

doi:10.1016/j.cplett.2008.10.024

Cited by 380 publications

(472 citation statements)

References 31 publications

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“…42,43 The theoretical modelling of electrochemical reactions is equally complex, as it needs to account for the effect of the solvent on the adsorbed intermediates, the highly charged electric field in the double layer, the free energy of the electrons in the solid and the free energy of the solvated reactants as a function of potential. [44][45][46][47][48][49][50][51][52][53][54] However, it turns out that the overall trends can be 7 ‡ We note that a fuel cell would probably be operated at potentials lower than 0.9 V, to maximise the power output. However, catalysts are typically benchmarked at 0.9 V to minimise artefacts from the measurements.…”

Section: Theoretical Trends In Activity For Pt and Its Alloysmentioning

confidence: 99%

Understanding the electrocatalysis of oxygen reduction on platinum and its alloys

Stephens

Bondarenko

Grønbjerg

et al. 2012

Energy Environ. Sci.

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1,085

1,024

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The high cost of low temperature fuel cells is to a large part dictated by the high loading of Pt required to catalyse the oxygen reduction reaction (ORR). Arguably the most viable route to decrease the Pt loading, and to hence commercialise these devices, is to improve the ORR activity of Pt by alloying it with other metals. In this perspective paper we provide an overview of the fundamentals underlying the reduction of oxygen on platinum and its alloys. We also report the ORR activity of Pt 5 La for the first time, which shows a 3.5-to 4.5-fold improvement in activity over Pt in the range 0.9 to 0.87 V, respectively. We employ angle resolved X-ray photoelectron spectroscopy and density functional theory calculations to understand the activity of Pt 5 La.

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Section: Theoretical Trends In Activity For Pt and Its Alloysmentioning

confidence: 99%

Understanding the electrocatalysis of oxygen reduction on platinum and its alloys

Stephens

Bondarenko

Grønbjerg

et al. 2012

Energy Environ. Sci.

Self Cite

1,085

1,024

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“…Experimentally the position of the VBM and CBM relative to the standard hydrogen electrode (SHE) is measured by capacitance or photocurrent measurements. 104 Both methods lead to a value for the flat-band potential relative to a reference electrode. Electron affinities may be linked to flat-band potentials, based on the difference in energy from the Fermi energy to the CBM in the bulk of the semiconductor and the band offset due to the semiconductor/electrolyte interface.…”

Section: Electron Affinities and Ionization Potentials Of Binary Nitrmentioning

confidence: 99%

Hybrid functional investigations of band gaps and band alignments for AlN, GaN, InN, and InGaN

Moses

Miao

Yan

et al. 2011

The Journal of Chemical Physics

290

231

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Band gaps and band alignments for AlN, GaN, InN, and InGaN alloys are investigated using density functional theory with the with the Heyd-Scuseria-Ernzerhof {HSE06 [J. Heyd, G. E. Scuseria, and M. Ernzerhof, J. Chem. Phys. 134, 8207 (2003); 124, 219906 (2006)]} XC functional. The band gap of InGaN alloys as a function of In content is calculated and a strong bowing at low In content is found, described by bowing parameters 2.29 eV at 6.25% and 1.79 eV at 12.5%, indicating the band gap cannot be described by a single composition-independent bowing parameter. Valence-band maxima (VBM) and conduction-band minima (CBM) are aligned by combining bulk calculations with surface calculations for nonpolar surfaces. The influence of surface termination [(1100) mplane or (1120) a-plane] is thoroughly investigated. We find that for the relaxed surfaces of the binary nitrides the difference in electron affinities between m-and a-plane is less than 0.1 eV. The absolute electron affinities are found to strongly depend on the choice of XC functional. However, we find that relative alignments are less sensitive to the choice of XC functional. In particular, we find that relative alignments may be calculated based on Perdew-Becke-Ernzerhof [J. P. Perdew, K. Burke, and M. Ernzerhof, Phys. Rev. Lett. 134, 3865 (1996)] surface calculations with the HSE06 lattice parameters. For InGaN we find that the VBM is a linear function of In content and that the majority of the band-gap bowing is located in the CBM. Based on the calculated electron affinities we predict that InGaN will be suited for water splitting up to 50% In content.

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“…In the future, it might be worth considering using explicit counter ions to compensate for the charge of electrode. 7 Alternatively, a combination of explicit water molecules and a continuum description of the electrochemical double-layer could be employed in the spirit of the modified Poisson-Boltzmann equation approach. [11][12][13] Having corrected the charged system absolute energies, the potential dependence of the grand canonical energies is obtained by fitting a parabola to the graph energy vs absolute potential.…”

Section: Construction Of Grand Canonical Energiesmentioning

confidence: 99%

“…Other suggested methods rely on extrapolating calculated energies from canonical, constant charge DFT simulations to constant electrode potential. Rossmeisl et al 7 have shown how reactions modeled with different supercell sizes can be used to recover activation energies in the limit of infinite system size, where the shift in potential vanishes. In this method, the electrode potential is controlled indirectly by varying the concentration of solvated protons.…”

Section: Introductionmentioning

confidence: 99%

“…Several methods [5][6][7][8][9][10][11][12][13] have been proposed for correcting quantum chemical calculations to constant electrode potential. The most elegant solution would be to treat electrons in the grand canonical ensemble, that is, to allow the number of electrons to change during the electronic structure self-consistency loop, which is equivalent to connecting the system to a fictitious potentiostat.…”

Section: Introductionmentioning

confidence: 99%

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Ab Initio Electrochemistry: Exploring the Hydrogen Evolution Reaction on Carbon Nanotubes

Holmberg

Laasonen

2015

J. Phys. Chem. C

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Density functional theory (DFT) was employed to investigate the hydrogen evolution reaction (HER) on pristine and nitrogen doped carbon nanotubes (CNTs) in acidic solution. As the reaction is an electrocatalytic surface reaction, an accurate description of HER requires performing simulations under constant electrode potential conditions. To this end, we examined HER at several electrode charges allowing us to determine grand canonical activation energies as a continuous function of electrode potential. By studying the elementary steps of HER -the Volmer, Tafel and Heyrovsky reactions -and by considering hydrogen coverage effects, we found that the Volmer-Heyrovsky mechanism is the predominant HER mechanism on CNTs with the Heyrovsky step being rate-determining. Our results indicated that CNTs are electrochemically active towards HER, which seen as a decrease in activation energies with growing electrode potential, but that the activity is lower than on platinum matching experimental data.Substitutional nitrogen doping did not improve HER activity, and further research is required to determine which nitrogen configurations contribute to the enhanced catalytic activity observed for experimental NCNTs.

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Modeling the electrified solid–liquid interface

Cited by 380 publications

References 31 publications

Understanding the electrocatalysis of oxygen reduction on platinum and its alloys

Understanding the electrocatalysis of oxygen reduction on platinum and its alloys

Hybrid functional investigations of band gaps and band alignments for AlN, GaN, InN, and InGaN

Ab Initio Electrochemistry: Exploring the Hydrogen Evolution Reaction on Carbon Nanotubes

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