Lifting the discrepancy between experimental results and the theoretical predictions for the catalytic activity of RuO<sub>2</sub>(110) towards oxygen evolution reaction

Divanis, Spyridon; Frandsen, Adrian; Kutlusoy, Tuğçe

doi:10.1039/d1cp02999a

Cited by 17 publications

(20 citation statements)

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“…In Ref. [16c] the scaling was found to be G ads (*O 2 +H b )≈ G ads (*O+H b )+2.7 eV for RuO 2 . To investigate if this relationship holds on our HEO, the energies of *O+H b and *O 2 +H b are calculated for 75 different adsorption sites.…”

Section: Resultsmentioning

confidence: 98%

Theoretical Optimization of Compositions of High‐Entropy Oxides for the Oxygen Evolution Reaction**

Svane¹

2022

Angew Chem Int Ed

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High‐entropy oxides are oxides consisting of five or more metals incorporated in a single lattice, and the large composition space suggests that properties of interest can be readily optimised. For applications within catalysis, the different local atomic environments result in a distribution of binding energies for the catalytic intermediates. Using the oxygen evolution reaction on the rutile (110) surface as example, here we outline a strategy for the theoretical optimization of the composition. Density functional theory calculations performed for a limited number of sites are used to fit a model that predicts the reaction energies for all possible local atomic environments. Two reaction pathways are considered; the conventional pathway on the coordinatively unsaturated sites and an alternative pathway involving transfer of protons to a bridging oxygen. An explicit model of the surface is constructed to describe the interdependency of the two pathways and identify the composition that maximizes catalytic activity.

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Section: Resultsmentioning

confidence: 98%

Theoretical Optimization of Compositions of High‐Entropy Oxides for the Oxygen Evolution Reaction**

Svane¹

2022

Angew Chem Int Ed

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“…We examined an alternative OER mechanism , where H 2 O is first adsorbed in an additional chemical step, passing the proton to a nearby O br (cf. Scheme S1).…”

Section: Resultsmentioning

confidence: 99%

Coordination Inversion of the Tetrahedrally Coordinated Ru_4f Surface Complex on RuO₂(100) and Its Decisive Role in the Anodic Corrosion Process

Heß

Over

2023

ACS Catal.

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The c(2 × 2) reconstruction of RuO 2 (100) leads to unusual and flexible surface functionality in the form of a tetrahedrally coordinated Ru 4f surface complex with distinct chemical properties that are important for the anodic activity and stability in water electrolysis. We employ first-principles methods based on density functional theory calculations to elucidate the hybridization of this Ru 4f surface species and its rich coordination chemistry. Under oxygen evolution reaction (OER) conditions, the consecutive breaking of structural Ru 4f −O back bonds is shown to proceed via the back side attack of Ru 4f (akin to the Walden inversion) by dissociative water adsorption and the release of two proton/electron pairs. This inversion step of the coordination environment of a surface transition metal cation is considered to be the key step in the anodic dissolution process. Oxygen evolution over Ru 4f on RuO 2 (100)−c(2 × 2) competes with its dissolution. From ab initio thermodynamics, the inherent OER activity over Ru 4f is shown to be lower than that of Ru surface sites on the unreconstructed RuO 2 (100), while the dissolution propensity of the Ru 4f surface complex is higher. This finding calls into question the frequently stated hypothesis that higher activity is correlated with a lower stability of the active center.

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“…The only difference is that we have drawn the peroxide intermediate, *OOH, with the hydrogen atom abstracted to a neighboring surface-bound oxygen atom, as has been proposed to take place on Ru(110), stabilizing this intermediate and lowering the OER overpotential. 29,41,42 We have labelled the peroxide intermediate as the “active state” or S RDS , *O as S RDS-1 , and *OH as S RDS-2 based on the analysis in the first article of this series. 35 The destabilized state that we propose as the link between labelled oxygen evolution and metal dissolution is indicated at the start of the middle row.…”

Section: Discussionmentioning

confidence: 99%

The low overpotential regime of acidic water oxidation part II: trends in metal and oxygen stability numbers

Scott

Sørensen

Rao

et al. 2022

Energy Environ. Sci.

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Lifting the discrepancy between experimental results and the theoretical predictions for the catalytic activity of RuO₂(110) towards oxygen evolution reaction

Abstract: Developing new efficient catalyst materials for the oxygen evolution reaction (OER) is essential for widespread proton exchange membrane water electrolyzer use. Both RuO2(110) and IrO2(110) have been shown to be...

Cited by 17 publications

References 30 publications

Theoretical Optimization of Compositions of High‐Entropy Oxides for the Oxygen Evolution Reaction**

Theoretical Optimization of Compositions of High‐Entropy Oxides for the Oxygen Evolution Reaction**

Coordination Inversion of the Tetrahedrally Coordinated Ru_4f Surface Complex on RuO₂(100) and Its Decisive Role in the Anodic Corrosion Process

The low overpotential regime of acidic water oxidation part II: trends in metal and oxygen stability numbers

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Lifting the discrepancy between experimental results and the theoretical predictions for the catalytic activity of RuO2(110) towards oxygen evolution reaction

Abstract: Developing new efficient catalyst materials for the oxygen evolution reaction (OER) is essential for widespread proton exchange membrane water electrolyzer use. Both RuO2(110) and IrO2(110) have been shown to be...

Cited by 17 publications

References 30 publications

Theoretical Optimization of Compositions of High‐Entropy Oxides for the Oxygen Evolution Reaction**

Theoretical Optimization of Compositions of High‐Entropy Oxides for the Oxygen Evolution Reaction**

Coordination Inversion of the Tetrahedrally Coordinated Ru4f Surface Complex on RuO2(100) and Its Decisive Role in the Anodic Corrosion Process

The low overpotential regime of acidic water oxidation part II: trends in metal and oxygen stability numbers

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Resources

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Lifting the discrepancy between experimental results and the theoretical predictions for the catalytic activity of RuO₂(110) towards oxygen evolution reaction

Coordination Inversion of the Tetrahedrally Coordinated Ru_4f Surface Complex on RuO₂(100) and Its Decisive Role in the Anodic Corrosion Process