Universality in Oxygen Evolution Electrocatalysis on Oxide Surfaces

Man, Isabela Costinela; Su, Hai‐Yan; Calle‐Vallejo, Federico; Hansen, Heine Anton; Martínez, José I.; İnoğlu, Nilay; Kitchin, John R.; Jaramillo, Thomas F.; Nørskov, Jens K.; Rossmeisl, Jan

doi:10.1002/cctc.201000397

Cited by 3,577 publications

(4,854 citation statements)

References 48 publications

(55 reference statements)

Supporting

239

Mentioning

4,367

Contrasting

Unclassified

Order By: Relevance

“…Increasing the oxygen content from the Ho to Pr double perovskite leads to a greater number of Co 3 þ in O h symmetry at the expense of C 4v symmetry, whereas the accompanied increase of the Co oxidation state reduces the number of Co 2 þ and increases the number of Co 3 þ and Co 4 þ . By a first approximation, these double perovskites were selected to have the following spin states based on previous studies 20,23,24 : Co 2 þ (3d 7 ) having high spin in the C 4v symmetry because of polarizability and steric issues 25 5 ) stabilized in high spin in the O h symmetry 26 ( Supplementary Fig. S9).…”

Section: Oer Activity Measurementsmentioning

confidence: 99%

“…Sabatier's principle, which qualitatively describes that high catalytic activity can be obtained when adsorbed species bind to the surface neither too strongly nor too weakly, has been instrumental to fundamental understanding of OER mechanisms and the development of highly active catalysts. Unfortunately, the binding strength of oxygen molecules and reaction intermediate species 6,7 is difficult to assess experimentally. Instead, experimental studies have correlated with the intrinsic OER activities of transition metal oxides with parameters [8][9][10] that can be estimated and measured from experiments such as the e g orbital filling of transition metal ions 10 .…”

mentioning

confidence: 99%

See 1 more Smart Citation

Double perovskites as a family of highly active catalysts for oxygen evolution in alkaline solution

et al. 2013

View full text Add to dashboard Cite

The electronic structure of transition metal oxides governs the catalysis of many central reactions for energy storage applications such as oxygen electrocatalysis. Here we exploit the versatility of the perovskite structure to search for oxide catalysts that are both active and stable. We report double perovskites (Ln 0.5 Ba 0.5 )CoO 3 À d (Ln ¼ Pr, Sm, Gd and Ho) as a family of highly active catalysts for the oxygen evolution reaction upon water oxidation in alkaline solution. These double perovskites are stable unlike pseudocubic perovskites with comparable activities such as Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3 À d which readily amorphize during the oxygen evolution reaction. The high activity and stability of these double perovskites can be explained by having the O p-band centre neither too close nor too far from the Fermi level, which is computed from ab initio studies.

show abstract

Section: Oer Activity Measurementsmentioning

confidence: 99%

mentioning

confidence: 99%

Double perovskites as a family of highly active catalysts for oxygen evolution in alkaline solution

et al. 2013

View full text Add to dashboard Cite

show abstract

“…In this way the same minimal potential (1.23 V at pH = 0, NHE) can drive all of the PCET steps, avoiding thermodynamic barriers due to uneven stability of some intermediates. For a wide class of crystalline metal and metal-oxide surfaces, the binding energies of metal-aquo/hydroxo and oxo species are shown to depend linearly one to another (32,33). As a result, the free energy of each oxidation (ΔG i in Eqs.…”

Section: Atomistic and Thermodynamic Origins Of Catalytic Efficiency:mentioning

confidence: 99%

Water oxidation surface mechanisms replicated by a totally inorganic tetraruthenium–oxo molecular complex

Piccinin

Sartorel

Aquilanti

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

106

View full text Add to dashboard Cite

Solar-to-fuel energy conversion relies on the invention of efficient catalysts enabling water oxidation through low-energy pathways. Our aerobic life is based on this strategy, mastered by the natural Photosystem II enzyme, using a tetranuclear Mn-oxo complex as oxygen evolving center. Within artificial devices, water can be oxidized efficiently on tailored metal-oxide surfaces such as RuO 2 . The quest for catalyst optimization in vitro is plagued by the elusive description of the active sites on bulk oxides. Although molecular mimics of the natural catalyst have been proposed, they generally suffer from oxidative degradation under multiturnover regime. Here we investigate a nano-sized Ru 4 -polyoxometalate standing as an efficient artificial catalyst featuring a totally inorganic molecular structure with enhanced stability. Experimental and computational evidence reported herein indicates that this is a unique molecular species mimicking oxygenic RuO 2 surfaces. Ru 4 -polyoxometalate bridges the gap between homogeneous and heterogeneous water oxidation catalysis, leading to a breakthrough system. Density functional theory calculations show that the catalytic efficiency stems from the optimal distribution of the free energy cost to form reaction intermediates, in analogy with metal-oxide catalysts, thus providing a unifying picture for the two realms of water oxidation catalysis. These correlations among the mechanism of reaction, thermodynamic efficiency, and local structure of the active sites provide the key guidelines for the rational design of superior molecular catalysts and composite materials designed with a bottom-up approach and atomic control.artificial photosynthesis | ab initio simulations | X-ray absorption spectroscopy | electrocatalysis P hotocatalytic water splitting offers a bioinspired strategy for replacing fossil fuels with clean energy vectors (1-3). The overall reaction entails a sequence of light-promoted electron and proton transfers coupled with cleavage and formation of molecular bonds, ultimately splitting H 2 O molecules into O 2 and H 2 . The application of such technology for a viable solar-fuel economy is at the forefront of a very intense research effort. The main issue is the design and optimization of innovative catalysts enabling the half reaction of water oxidation (2H 2 O → O 2 + 4H + + 4e − ) (1) at low overpotential, high turnover frequencies, and longterm operation stability. Considering its high thermodynamic cost [E 0 = −1.23 V at pH = 0 vs. normal hydrogen electrode (NHE)] and mechanistic complexity, water oxidation catalysis (WOC) poses severe challenges for artificial photosynthesis applications.In plants, water oxidation is catalyzed by the Mn 4 CaO 4 oxygen evolving complex of Photosystem II (PSII) enzymes. The natural catalyst exhibits a functional asset of four redox active metal centers with adjacent μ-oxo bridges to enable water oxidation with a maximal turnover frequency of 400 s −1 per O 2 molecule (4). The drawback lies in the intrinsic weakness of the biol...

show abstract

“…Substantial efforts have thus been devoted to lowering the costs of the electrodes necessary for water splitting 9,10 . Recent theoretical works exposed the mechanistic features of the oxygen evolution reaction (OER) 11,12 , taking place at the anodes of electrolyzers, in which water is oxidized to produce molecular oxygen and protons. These insights motivated several reports on earth-abundant and highly-efficient OER anode materials that typically work at high pH 13,14 .…”

Section: Introductionmentioning

confidence: 99%

Interfacial water reorganization as a pH-dependent descriptor of the hydrogen evolution rate on platinum electrodes

et al. 2017

View full text Add to dashboard Cite

The hydrogen evolution on platinum is a milestone reaction in electrocatalysis as well as an important reaction towards sustainable energy storage. Remarkably, the pH dependent kinetics of this reaction is not yet fully understood. Here, we present a detailed kinetic study of the hydrogen adsorption and evolution reaction on Pt(111) in a wide pH range. Impedance and Tafel slope measurements show that the hydrogen adsorption and hydrogen evolution are both slow in alkaline media, which is consistent with the observation of a shift in the rate-determining step for H2 evolution.Adding nickel to the Pt(111) surface lowers the barrier for the hydrogen adsorption rate in alkaline solutions and thereby enhances the hydrogen evolution rate. These observations are explained by a new model which highlights the role of the reorganization of interfacial water to accommodate charge transfer through the electric double layer, the energetics of which is controlled by how strongly water interacts with the interfacial field. The new model is supported by laser-induced temperature-jump measurements. Our model sheds new light on the origin of the slow kinetics for the hydrogen evolution reaction in alkaline media.

show abstract

Universality in Oxygen Evolution Electrocatalysis on Oxide Surfaces

Cited by 3,577 publications

References 48 publications

Double perovskites as a family of highly active catalysts for oxygen evolution in alkaline solution

Double perovskites as a family of highly active catalysts for oxygen evolution in alkaline solution

Water oxidation surface mechanisms replicated by a totally inorganic tetraruthenium–oxo molecular complex

Interfacial water reorganization as a pH-dependent descriptor of the hydrogen evolution rate on platinum electrodes

Contact Info

Product

Resources

About