Gas‐phase errors affect DFT‐based electrocatalysis models of oxygen reduction to hydrogen peroxide

Almeida, Michell O.; Kolb, Manuel J.; Lanza, Marcos R.V.; Illas, Francesc; Calle‐Vallejo, Federico

doi:10.1002/celc.202200505

Cited by 9 publications

(12 citation statements)

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“…The free-energy diagrams allow determining the descriptor G max (η = 0 V) for the OER and PFR, using the free-energy span model from the RI with the lowest free energy to the RI with highest free energy, as introduced in section . For an accurate determination of the PFR free-energy landscape, gas-phase error corrections are called for, as discussed by Calle-Vallejo and co-workers . In the presented approach, we make use of the experimental equilibrium potential rather than calculate the H 2 O 2 molecule because the latter may result in an inaccurate equilibrium potential for the PFR.…”

Section: Application Of G Max(η)mentioning

confidence: 99%

“…For an accurate determination of the PFR free-energy landscape, gas-phase error corrections are called for, as discussed by Calle-Vallejo and co-workers. 121 In the presented approach, we make use of the experimental equilibrium potential rather than calculate the H 2 O 2 molecule because the latter may result in an inaccurate equilibrium potential for the PFR.…”

Section: Application Of G Max (η)mentioning

confidence: 99%

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Materials Screening by the Descriptor G_max(η): The Free-Energy Span Model in Electrocatalysis

Razzaq

Exner

2023

ACS Catal.

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To move from fossil-based energy resources to a society based on renewables, electrode materials free of precious noble metals are required to efficiently catalyze electrochemical processes in fuel cells, batteries, or electrolyzers. Materials screening operating at minimal computational cost is a powerful method to assess the performance of potential electrode compositions based on heuristic concepts. While the thermodynamic overpotential in combination with the volcano concept refers to the most popular descriptor-based analysis in the literature, this notion cannot reproduce experimental trends reasonably well. About two years ago, the concept of G max (η), based on the idea of the free-energy span model, has been proposed as a universal approach for the screening of electrocatalysts. In contrast to other available descriptor-based methods, G max (η) factors overpotential and kinetic effects by a dedicated evacuation scheme of adsorption free energies into an analysis of trends. In the present perspective, we discuss the application of G max (η) to different electrocatalytic processes, including the oxygen evolution and reduction reactions, the nitrogen reduction reaction, and the selectivity problem of the competing oxygen evolution and peroxide formation reactions, and we outline the advantages of this screening approach over previous investigations.

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Section: Application Of G Max(η)mentioning

confidence: 99%

Section: Application Of G Max (η)mentioning

confidence: 99%

Materials Screening by the Descriptor G_max(η): The Free-Energy Span Model in Electrocatalysis

Razzaq

Exner

2023

ACS Catal.

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“…The DFT-predicted reduction potentials for halothane are almost error-free compared to the experimental peak potentials. While the value for BrBz is the farthest from its experimental counterpart with a difference of ∼0.3 eV, it is in the reported range of errors for DFT-calculated free energies. , The slightly higher discrepancy in BrBz may come from kinetic reasons as well.…”

Section: Resultsmentioning

confidence: 69%

“…While the value for BrBz is the farthest from its experimental counterpart with a difference of ∼0.3 eV, it is in the reported range of errors for DFT-calculated free energies. 52,53 The slightly higher discrepancy in BrBz may come from kinetic reasons as well.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Tailoring Ag Electron Donating Ability for Organohalide Reduction: A Bilayer Electrode Design

Abbaspourtamijani,

Chakraborty,

White

et al. 2023

Langmuir

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Electrochemical reduction of organohalides provides a green approach in the reduction of environmental pollutants, the synthesis of new organic molecules, and many other applications. The presence of a catalytic electrode can make the process more energetically efficient. Ag is known to be a very good electrode for the reduction of a wide range of organohalides. Herein, we examine the elementary adsorption and reaction steps that occur on Ag and the changes that result from changes in the Ag-coated metal, strain in Ag, solvent, and substrate geometry. The results are used to develop an electrode design strategy that can possibly be used to further increase the catalytic activity of pure Ag electrodes. We have shown how epitaxially depositing one to three layers of Ag on catalytically inert or less active support metal can increase the surface electron donating ability, thus increasing the adsorption of organic halide and the catalytic activity. Many factors, such as molecular geometry, lattice mismatches, work function, and solvents, contribute to the adsorption of organic halide molecules over the bilayer electrode surface. To isolate and rank these factors, we examined three model organic halides, namely, halothane, bromobenzene (BrBz), and benzyl bromide (BzBr) adsorption on Ag/metal (metal = Au, Bi, Pt, and Ti) bilayer electrodes in both vacuum and acetonitrile (ACN) solvent. The different metal supports offer a range of lattice mismatches and work function differences with Ag. Our calculations show that the surface of Ag becomes more electron donating and accessible to adsorption when it forms a bilayer with Ti as it has a lower work function and almost zero lattice mismatch with Ag. We believe this study will help to increase the electron donating ability of the Ag surface by choosing the right metal support, which in turn can improve the catalytic activity of the working electrode.

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“…Instead of using the energy of CH 4 (g) in the gas phase, as would be the case following the standard CBH approach, it is assumed that CH 4 is physisorbed on the surface, and we use CH 4 * accordingly. A higher amount of error cancellation can be expected when assuming physisorbed species since the typical DFT functionals that perform well for adsorbates are often less accurate at predicting gas-phase energies. ,− Following the formalism, the adsorption site is treated as a single Pt atom that can have either single, double, or triple bonds that can be saturated with H, too. The reaction is then balanced with the required amount of H 2 * .…”

Section: Methodsmentioning

confidence: 99%

Linking Experimental and Ab Initio Thermochemistry of Adsorbates with a Generalized Thermochemical Hierarchy

Kreitz

Abeywardane

Goldsmith

2023

J. Chem. Theory Comput.

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Enthalpies of formation of adsorbates are crucial parameters in the microkinetic modeling of heterogeneously catalyzed reactions since they quantify the stability of intermediates on the catalyst surface. This quantity is often computed using density functional theory (DFT), as more accurate methods are computationally still too expensive, which means that the derived enthalpies have a large uncertainty. In this study, we propose a new error cancellation method to compute the enthalpies of formation of adsorbates from DFT more accurately through a generalized connectivity-based hierarchy. The enthalpy of formation is determined through a hypothetical reaction that preserves atomistic and bonding environments. The method is applied to a data set of 60 adsorbates on Pt(111) with up to 4 heavy (non-hydrogen) atoms. Enthalpies of formation of the fragments required for the bond balancing reactions are based on experimental heats of adsorption for Pt(111). The comparison of enthalpies of formation derived from different DFT functionals using the isodesmic reactions shows that the effect of the functional is significantly reduced due to the error cancellation. Thus, the proposed methodology creates an interconnected thermochemical network of adsorbates that combines experimental with ab initio thermochemistry in a single and more accurate thermophysical database.

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Gas‐phase errors affect DFT‐based electrocatalysis models of oxygen reduction to hydrogen peroxide

Cited by 9 publications

References 0 publications

Materials Screening by the Descriptor G_max(η): The Free-Energy Span Model in Electrocatalysis

Materials Screening by the Descriptor G_max(η): The Free-Energy Span Model in Electrocatalysis

Tailoring Ag Electron Donating Ability for Organohalide Reduction: A Bilayer Electrode Design

Linking Experimental and Ab Initio Thermochemistry of Adsorbates with a Generalized Thermochemical Hierarchy

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Gas‐phase errors affect DFT‐based electrocatalysis models of oxygen reduction to hydrogen peroxide

Cited by 9 publications

References 0 publications

Materials Screening by the Descriptor Gmax(η): The Free-Energy Span Model in Electrocatalysis

Materials Screening by the Descriptor Gmax(η): The Free-Energy Span Model in Electrocatalysis

Tailoring Ag Electron Donating Ability for Organohalide Reduction: A Bilayer Electrode Design

Linking Experimental and Ab Initio Thermochemistry of Adsorbates with a Generalized Thermochemical Hierarchy

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Materials Screening by the Descriptor G_max(η): The Free-Energy Span Model in Electrocatalysis

Materials Screening by the Descriptor G_max(η): The Free-Energy Span Model in Electrocatalysis