Water oxidation catalysts based on abundant 1st row transition metals

Singh, Archana; Spiccia, Leone

doi:10.1016/j.ccr.2013.02.027

Cited by 378 publications

(250 citation statements)

References 201 publications

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“…[30][31][32] Several reviews have been published from different perspectives, [33][34][35][36] although the literature on the use of first row transition metal oxo/hydroxides for water oxidation is so vast that it is an impossible task to classify and put into context all the results. After decades of research, there are still many open controversies regarding function, stability and performance, with contradictory data available.…”

Section: Introductionmentioning

confidence: 99%

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Water Oxidation at Electrodes Modified with Earth‐Abundant Transition‐Metal Catalysts

2014

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Section: Introductionmentioning

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“…Our analysis of their pros and cons will be complementary to more general recent reviews, focused on another aspects of this crucial challenge. [17][18][19][20][21][22][23] …”

Section: Introductionmentioning

confidence: 99%

Water Oxidation at Electrodes Modified with Earth‐Abundant Transition‐Metal Catalysts

2014

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“…1 In addition, the underlying four-electron/fourproton water oxidation is of biological interest since such reaction takes place at the oxygenevolving Mn 4 Ca complex of photosystem II in green plants and algae. 2 Significant developments in the field of water oxidation catalysis have emerged over the last few years, including both molecular systems 3,4 and for metal-oxide catalysts. 5,6,7 Water oxidation catalysts (WOCs) benefit from molecular toolkit that exploit electronic and steric effects,and can be efficiently combined to generate extremely fast, oxidatively rugged catalysts.…”

Section: Introductionmentioning

confidence: 99%

Behavior of the Ru-bda Water Oxidation Catalyst Covalently Anchored on Glassy Carbon Electrodes

et al. 2015

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, (N-N 2 is 4-(pyridin-4-yl) benzenediazonium) in acetone allows grafting it onto graphite electrodes (GC). Multiple cycling voltammetric experiments on the same electrode generates a new hybrid material GC-4 with the Ru-aqua complex anchored on the graphite surface. GC-4. While the complex anchored on the graphite surface is an active water oxidation catalyst, as characterized at pH = 7.0 via electrochemical techniques and XAS, it has worse performance than in the homogeneous phase and decomposes to form RuO 2 at the electrode surface. However, we find that the resulting metal oxide attached to the GC electrode, GC-RuO 2 , is a very fast and rugged heterogeneous water oxidation catalyst with TOF i s of 300 s -1 and TONs >45000. The observed performance is comparable to the best electrocatalysts reported, so far, at neutral pH. Keywordswater oxidation catalysis, electrocatalysis, water splitting, Ru complexes, modified graphite electrodes, heterogeneous water oxidation catalysis, RuO 2 . TOCThe performance of new hybrid materials based on molecular Ru-bda type of complexes anchored on graphitic surfaces as water oxidation catalysts, is described. The nature of the active species is uncovered based on electrochemical techniques and XAS spectroscopy.

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“…NiFe oxyhydroxide | oxygen evolution reaction | electrocatalysis | spectroelectrochemistry | density functional theory T he photoelectrochemical conversion of water into O 2 and H 2 is a major focus of energy storage and conversion efforts (1)(2)(3)(4), with significant attention directed toward development of efficient catalysts for water oxidation and reduction. Such catalysts should operate at low overpotential, exhibit high selectivity, and be composed of earth-abundant materials.…”

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confidence: 99%

Characterization of NiFe oxyhydroxide electrocatalysts by integrated electronic structure calculations and spectroelectrochemistry

Goldsmith

Harshan

Gerken

et al. 2017

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

183

161

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NiFe oxyhydroxide materials are highly active electrocatalysts for the oxygen evolution reaction (OER), an important process for carbon-neutral energy storage. Recent spectroscopic and computational studies increasingly support iron as the site of catalytic activity but differ with respect to the relevant iron redox state. A combination of hybrid periodic density functional theory calculations and spectroelectrochemical experiments elucidate the electronic structure and redox thermodynamics of Ni-only and mixed NiFe oxyhydroxide thin-film electrocatalysts. The UV/visible light absorbance of the Ni-only catalyst depends on the applied potential as metal ions in the film are oxidized before the onset of OER activity. In contrast, absorbance changes are negligible in a 25% Fe-doped catalyst up to the onset of OER activity. First-principles calculations of proton-coupled redox potentials and magnetizations reveal that the Ni-only system features oxidation of Ni 2+ to Ni 3+ , followed by oxidation to a mixed Ni 3+/4+ state at a potential coincident with the onset of OER activity. Calculations on the 25% Fedoped system show the catalyst is redox inert before the onset of catalysis, which coincides with the formation of Fe 4+ and mixed Ni oxidation states. The calculations indicate that introduction of Fe dopants changes the character of the conduction band minimum from Ni-oxide in the Ni-only to predominantly Fe-oxide in the NiFe electrocatalyst. These findings provide a unified experimental and theoretical description of the electrochemical and optical properties of Ni and NiFe oxyhydroxide electrocatalysts and serve as an important benchmark for computational characterization of mixedmetal oxidation states in heterogeneous catalysts.NiFe oxyhydroxide | oxygen evolution reaction | electrocatalysis | spectroelectrochemistry | density functional theory T he photoelectrochemical conversion of water into O 2 and H 2 is a major focus of energy storage and conversion efforts (1-4), with significant attention directed toward development of efficient catalysts for water oxidation and reduction. Such catalysts should operate at low overpotential, exhibit high selectivity, and be composed of earth-abundant materials. Commercial electrolyzers typically use transition-metal-oxide electrocatalysts for the oxygen evolution reaction (OER) (5, 6), and nickel, nickel-iron, and other mixed-metal oxides are especially effective under alkaline conditions (7,8). Despite the importance and potential future impact of these materials, many features of their catalytic mechanism are poorly understood.Nickel oxyhydroxide has long been associated with OER electrocatalysis (9, 10); however, much of the activity in this material has been shown to arise from the presence of Fe impurities (7, 11). This conclusion complements extensive independent studies demonstrating the effectiveness of NiFebased oxide and oxyhydroxide materials as OER electrocatalysts (12-14), including a survey of nearly 3,500 mixed-metal-oxide compositions, which drew attentio...

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Water oxidation catalysts based on abundant 1st row transition metals

Cited by 378 publications

References 201 publications

Water Oxidation at Electrodes Modified with Earth‐Abundant Transition‐Metal Catalysts

Water Oxidation at Electrodes Modified with Earth‐Abundant Transition‐Metal Catalysts

Behavior of the Ru-bda Water Oxidation Catalyst Covalently Anchored on Glassy Carbon Electrodes

Characterization of NiFe oxyhydroxide electrocatalysts by integrated electronic structure calculations and spectroelectrochemistry

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