Insights into the durability of Co–Fe spinel oxygen evolution electrocatalysts<i>via operando</i>studies of the catalyst structure

Calvillo, Laura; Carraro, Francesco; Vozniuk, Olena; Celorrio, Verónica; Nodari, Luca; Russell, Andrea E.; Debellis, Doriana; Fermı́n, David J.; Cavani, Fabrizio; Agnoli, Stefano; Granozzi, G.

doi:10.1039/c7ta10892c

Cited by 48 publications

(63 citation statements)

References 35 publications

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“…Other studies have not reported an increase in Fe oxidation state along with potential‐dependent shortening of the Fe−O bond in Co(Fe)O x H y , or Ni(Fe)O x H y , OER catalysts in alkaline solution . This is most likely due to differences in catalyst preparation.…”

Section: Figurementioning

confidence: 92%

“…solutions of Co(NO 3 ) 2 and FeCl 2 , leading to highly porous films where nearly every Co/Fe cation is exposed to the electrolyte . These films are completely transformed into the active oxyhydroxide phase under OER conditions thus making them superior samples for study compared to oxide phases where only the surface is electrochemically active . The deposition solution was then exchanged for 1 m KOH for electrochemical testing and XAS data collection.…”

Section: Figurementioning

confidence: 99%

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Operando X‐Ray Absorption Spectroscopy Shows Iron Oxidation Is Concurrent with Oxygen Evolution in Cobalt–Iron (Oxy)hydroxide Electrocatalysts

et al. 2018

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Iron cations are essential for the high activity of nickel and cobalt-based (oxy)hydroxides for the oxygen evolution reaction, but the role of iron in the catalytic mechanism remains under active investigation. Operando Xray absorption spectroscopya nd density functional theory calculations are used to demonstrate partial Fe oxidation and ashortening of the FeÀObond length during oxygen evolution on Co(Fe)O x H y .C obalt oxidation during oxygen evolution is only observed in the absence of iron. These results demonstrate adifferent mechanism for water oxidation in the presence and absence of iron and support the hypothesis that oxidized iron species are involved in water-oxidation catalysis on Co-(Fe)O x H y .

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Section: Figurementioning

confidence: 92%

Section: Figurementioning

confidence: 99%

Operando X‐Ray Absorption Spectroscopy Shows Iron Oxidation Is Concurrent with Oxygen Evolution in Cobalt–Iron (Oxy)hydroxide Electrocatalysts

et al. 2018

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“…The reforming of bioethanol, and in general of bioalcohols, to syngas, has been the object of several investigations during the latest years. This reaction can be carried out in the chemical-loop mode, that is, by alternating the bioalcohol and steam over an O-carrier [129][130][131][132][133][134][135][136][137], the so-called chemical-loop reforming (CLR). Amongst the most promising materials, ferrospinels offer the advantage of a wide flexibility of composition, structural stability and tunable redox properties.…”

Section: Spinels As Catalysts For the Chemical-loop Reforming (Clr) Omentioning

confidence: 99%

“…Recent study on CoFe 2 O 4 and FeCo 2 O 4 as oxygen carrier materials was performed by Carraro et al [129,130]. During the reduction step with ethanol, FeCo 2 O 4 was reduced faster compared to CoFe 2 O 4 .…”

Section: Spinels As Catalysts For the Chemical-loop Reforming (Clr) Omentioning

confidence: 99%

“…Several uses of spinel-type mixed oxides as catalysts for a variety of reactions have been reported; Table 2 summarizes the main ones. [129][130][131][132][133][134][135][136][137] It is shown that most applications investigated are for the oxidation of organic substrates, for example, for the synthesis of aldehydes or acids. In the field of biomass valorization, worthy of note are the recent papers on the oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) with O 2 , and catalytic transformation involving bioalcohols, mainly bioethanol.…”

Section: Introductionmentioning

confidence: 99%

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Mixed-Oxide Catalysts with Spinel Structure for the Valorization of Biomass: The Chemical-Loop Reforming of Bioethanol

et al. 2018

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This short review reports on spinel-type mixed oxides as catalysts for the transformation of biomass-derived building blocks into chemicals and fuel additives. After an overview of the various methods reported in the literature for the synthesis of mixed oxides with spinel structure, the use of this class of materials for the chemical-loop reforming of bioalcohols is reviewed in detail. This reaction is aimed at the production of H 2 with intrinsic separation of C-containing products, but also is a very versatile tool for investigating the solid-state chemistry of spinels.

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Oxygen Evolution Reaction in Alkaline Environment: Material Challenges and Solutions

Xie

Yan

et al. 2022

Adv Funct Materials

239

151

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The oxygen evolution reaction (OER) generally exists in electrochemistry-enabled applications that are coupled with cathodic reactions like hydrogen evolution, carbon dioxide reduction, ammonia synthesis, and electrocatalytic hydrogenation. The OER heavily impacts the overall energy efficiency of these devices because the sluggish OER kinetics result in a huge overpotential, thus, a large amount of efficient catalysts are needed. The benchmark iridium and ruthenium (Ir/Ru)based materials (mostly used in acid media) are, however, significantly limited by their scarcity. Non-precious metal-based catalysts (NPMCs) have emerged as the most promising alternatives; however, they tend to degrade quickly under the harsh operating conditions of typical OER devices. Another challenge is the unsatisfying performance of OER catalysts when integrated in real-world devices. Herein, the OER active sites for three mainstream types of NPMCs including nonprecious transition metal oxides/(oxy)hydroxides, metal-free carbon materials, and hybrid non-precious metal and carbon composites are reviewed. In addition, possible degradation mechanisms for active sites and mitigation strategies are discussed in detail. This review also provides insights into the gaps between R&D of NPMCs for the OER and their applications in practical devices.

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Insights into the durability of Co–Fe spinel oxygen evolution electrocatalystsvia operandostudies of the catalyst structure

Abstract: Utilization ofin situ/operandotechniques for establishing the chemical/structural changes induced on Co–Fe spinels that determine their OER durability.

Cited by 48 publications

References 35 publications

Operando X‐Ray Absorption Spectroscopy Shows Iron Oxidation Is Concurrent with Oxygen Evolution in Cobalt–Iron (Oxy)hydroxide Electrocatalysts

Operando X‐Ray Absorption Spectroscopy Shows Iron Oxidation Is Concurrent with Oxygen Evolution in Cobalt–Iron (Oxy)hydroxide Electrocatalysts

Mixed-Oxide Catalysts with Spinel Structure for the Valorization of Biomass: The Chemical-Loop Reforming of Bioethanol

Oxygen Evolution Reaction in Alkaline Environment: Material Challenges and Solutions

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