Iridium-based complexes for water oxidation

Thomsen, Julianne M.; Huang, Daria L.; Crabtree, Robert H.; Brudvig, Gary W.

doi:10.1039/c5dt00863h

Cited by 159 publications

(122 citation statements)

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“…Recently, they showed that when molecular iridium dimer catalyst 3 was anchored to an ITO surface, a very low onset potential was found of only 14 mV as reported by the authors (Figure , 3@MO x ) . This dimeric complex presumably operates through the ROC mechanism . The dimeric nature of this type of iridium catalysts is also supported by kinetic analysis of the reaction progress .…”

Section: Experimental Examplesmentioning

confidence: 52%

“…Therefore, the WNA mechanism dominates, resulting in a higher overpotential. Another class of molecular catalysts with a very low overpotential are the iridium catalysts reported by Brudvig, Crabtree and co‐workers . Recently, they showed that when molecular iridium dimer catalyst 3 was anchored to an ITO surface, a very low onset potential was found of only 14 mV as reported by the authors (Figure , 3@MO x ) .…”

Section: Experimental Examplesmentioning

confidence: 74%

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Rational Design Rules for Molecular Water Oxidation Catalysts based on Scaling Relationships

Hessels

Detz

Koper

et al. 2017

Chemistry A European J

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Lowering the overpotential required for water oxidation is of paramount importance for the efficient production of carbon-neutral fuels. This article highlights the intrinsic influence of the water oxidation mechanism used by molecular catalysts on the theoretically achievable minimal overpotential, based on scaling relationships typically used for heterogeneous catalysts. Due to such scaling relationships, catalysts that operate through the water nucleophilic attack mechanism have a fundamental minimal overpotential of about 0.3 V, whereas those that follow the dinuclear radical oxo coupling mechanism should in principle be able to operate with a lower overpotential. Therefore, it is recommended to design catalysts operating through the latter mechanism to achieve very efficient water oxidation systems.

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Section: Experimental Examplesmentioning

confidence: 52%

Section: Experimental Examplesmentioning

confidence: 74%

Rational Design Rules for Molecular Water Oxidation Catalysts based on Scaling Relationships

Hessels

Detz

Koper

et al. 2017

Chemistry A European J

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“…Successively, many other molecular Ir WOCs were reported, and many excellent and exhaustive reviews recently appeared in the literature , , . Herein, the focus is on the stability and activity of Ir WOCs, two strictly interlocked and crucial aspects.…”

Section: Molecular Ir Wocsmentioning

confidence: 99%

The Middle‐Earth between Homogeneous and Heterogeneous Catalysis in Water Oxidation with Iridium

Macchioni

2018

Eur J Inorg Chem

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Water oxidation (WO) is considered the ideal reaction to provide electrons and protons for the photo‐ and electrosynthesis of renewable fuels, generating exclusively O2 as a benign by‐product. Besides being demanding from the thermodynamic point of view, WO is also extremely difficult from the kinetic one. This has caused an explosion of interest for developing efficient water oxidation catalysts (WOCs). WOCs based on noble metals usually exhibit much better performance. For that reason, parallel to the search for efficient non‐noble metal WOCs, many efforts are directed toward noble‐metal atom economy in WOCs. Three strategies have been proposed to minimizing the atomic contents of noble metals: (1) exploiting molecular WOCs, under the assumption that all metal centers are catalytically active, differently from what happens in heterogeneous WOCs; (2) anchoring a well‐defined molecular WOC onto a suitable support, thus obtaining a heterogenized WOC, combining the positive aspects of homogeneous and heterogeneous catalysis; (3) diluting active metal centers in a suitable material with features that maximize the metal‐accessibility and performance. Herein, the results of our efforts aimed at pursuing all three strategies for developing efficient WOCs based on iridium are reviewed.

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“…The OER is important for many renewable energy conversion technologies, such as photoelectrochemical cells, regenerative fuel cells, and electrolyzers [1,4,5]. In acid systems, Ir and Ru-based oxides are common catalysts for the OER, while in alkaline environments non-precious transition metal oxides based on Ni, Fe, and Co are commonly employed [6][7][8][9][10]. In all cases, OER catalysts suffer from considerable overpotential losses, limiting the efficiency of hydrogen generation by water electrolysis processes [11].…”

Section: Introductionmentioning

confidence: 99%

Transition Metal-Modified Zirconium Phosphate Electrocatalysts for the Oxygen Evolution Reaction

et al. 2017

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Zirconium phosphate (ZrP), an inorganic layered nanomaterial, is currently being investigated as a catalyst support for transition metal-based electrocatalysts for the oxygen evolution reaction (OER). Two metal-modified ZrP catalyst systems were synthesized: metal-intercalated ZrP and metal-adsorbed ZrP, each involving Fe(II), Fe(III), Co(II), and Ni(II) cations. Fourier transform infrared spectroscopy, X-ray powder diffraction, thermogravimetric analysis, and X-ray photoelectron spectroscopy were used to characterize the composite materials and confirm the incorporation of the metal cations either between the layers or on the surface of ZrP. Both types of metal-modified systems were examined for their catalytic activity for the OER in 0.1 M KOH solution. All metal-modified ZrP systems were active for the OER. Trends in activity are discussed as a function of the molar ratio in relation to the two types of catalyst systems, resulting in overpotentials for metal-adsorbed ZrP catalysts that were less than, or equal to, their metal-intercalated counterparts.

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Iridium-based complexes for water oxidation

Abstract: Activation of organometallic Ir precatalysts can yield either homogeneous or heterogeneous water-oxidation catalysts with very high activity.

Cited by 159 publications

References 100 publications

Rational Design Rules for Molecular Water Oxidation Catalysts based on Scaling Relationships

Rational Design Rules for Molecular Water Oxidation Catalysts based on Scaling Relationships

The Middle‐Earth between Homogeneous and Heterogeneous Catalysis in Water Oxidation with Iridium

Transition Metal-Modified Zirconium Phosphate Electrocatalysts for the Oxygen Evolution Reaction

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