Ternary Ni-Co-Fe oxyhydroxide oxygen evolution catalysts: Intrinsic activity trends, electrical conductivity, and electronic band structure

Stevens, Michaela Burke; Enman, Lisa J.; Korkus, Ester Hamal; Zaffran, Jérémie; Trang, Christina D. M.; Asbury, James; Kast, Matthew G.; Toroker, Maytal Caspary; Boettcher, Shannon W.

doi:10.1007/s12274-019-2391-y

Cited by 155 publications

(130 citation statements)

References 71 publications

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“…Consistent with previous studies, we find that in the best acceptor sites the presence of Fe is essential . Fe‐containing acceptor sites are favored, as G(Acc‐H)−G(Acc)= G step4’ in Table S3–6 is typically around 1.23 eV for most of these.…”

Section: Resultssupporting

confidence: 90%

“…At the HSE06‐level, we obtain an overpotential of 1.09 eV, in line with the overpotential of 1.22 V obtained with a hybrid functional onto a system without two explicit waters . Such large overpotentials are a huge overestimation compared to experiments performed on pure NiOOH, with overpotentials of 0.4‐0.5 V around 1 mA.cm −2 . However, it is clear that both GGA+U and hybrid functionals are far off the experimental result.…”

Section: Resultssupporting

confidence: 75%

“…However, also other factors within mixed oxy hydroxides matter in OER performance assessments, such as the composition dependent conductivity, and reaction barriers which both increase the required overpotential. While reaction barriers can be computed, electronic conductivity is composition dependent and can be measured experimentally …”

Section: Discussionmentioning

confidence: 99%

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Oxygen Evolution on Metal‐oxy‐hydroxides: Beneficial Role of Mixing Fe, Co, Ni Explained via Bifunctional Edge/acceptor Route

2020

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Oxygen evolution reaction (OER) via mixed metal oxy hydroxides [M(O)(OH)] may take place on a large variety of possible active sites on the actual catalyst. A single site computational description assumes a 4‐step electrochemical mechanism with coupled H+/e− transfers between 4 intermediates (M‐*, M‐OH, M=O, M‐OOH). We also consider bifunctional routes, in which an unstable M‐OOH species converts via a proton shuttling pathway to a thermodynamically more favourable bare M‐* site, O2 and a hydrogenated acceptor site; the acceptor site takes up the proton forming a hydrogenated acceptor site after recombination with an electron from the catalyst material. Here, we combine pure metal γ‐M(O)(OH) edge sites (M=Fe, Co, Ni) with as proton‐acceptor sites different threefold coordinated oxygens on β‐(M,M’)(O)(OH) terraces (M,M’=Fe, Co, Ni). The acceptor sites on these terraces have of a M’2MO motif. Our combinatorial study results in a ranking of the bifunctional OER activity on a 3D‐volcano plot. By studying various bi‐ and tri‐metallic oxy hydroxide combinations, we show that their excellent experimental OER activity results from bifunctionality and provide a roadmap to construct innovative low overpotential OER catalysts.

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Section: Resultssupporting

confidence: 90%

Section: Resultssupporting

confidence: 75%

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Oxygen Evolution on Metal‐oxy‐hydroxides: Beneficial Role of Mixing Fe, Co, Ni Explained via Bifunctional Edge/acceptor Route

2020

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“…In conventional commercial production, Pt is the highest HER catalyst while RuO 2 is the optimal OER catalyst, nevertheless, the scarcity and costliness of those catalysts hinder their wide uses. [12,13] Accordingly, it is highly desired to develop efficient non-noble bifunctional catalysts for water splitting.Transition metal layered double hydroxides are considered to promising materials for OER to reduce the overpotential and promote electrolysis efficiency, [14][15][16][17][18] however, most of them have poor catalytic performance toward HER. As we all know, transition metal tetrathiomolybdate show remarkably efficient catalytic performance in HER.…”

mentioning

confidence: 99%

“…Transition metal layered double hydroxides are considered to promising materials for OER to reduce the overpotential and promote electrolysis efficiency, [14][15][16][17][18] however, most of them have poor catalytic performance toward HER. As we all know, transition metal tetrathiomolybdate show remarkably efficient catalytic performance in HER.…”

mentioning

confidence: 99%

Synergy of Cobalt Iron Tetrathiomolybdate Coated on Cobalt Iron Carbonate Hydroxide Hydrate Nanowire Arrays for Overall Water Splitting

et al. 2020

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Electrochemical water splitting is regarded as an ideal strategy for producing hydrogen energy. However, the ability to design efficient and durable noble-metal-free catalysts for decreasing the overpotential in the electrolysis process is in high demand.Here, it is demonstrated that cobalt iron carbonate hydroxide hydrate nanowire arrays on Ti mesh (CFOC/TM) obtained through a surface anion interchange method can lead to amorphous cobalt iron tetrathiomolybdate coated on crystalline cobalt iron carbonate hydroxide hydrate nanowire arrays on Ti mesh (CFMS@CFOC/TM), which can act as an efficient and durable water splitting electrocatalyst in alkaline media. CFMS@CFOC/TM shows good performance for the oxygen evolution and hydrogen evolution reactions, with the need for low overpotentials of 237 mV and 93 mV at 10 mA cm À 2 in 1.0 M KOH, respectively. As a 3D bifunctional electrode catalyst, it enables alkaline water splitting with excellent performance, achieving 10 mA cm À 2 at a voltage of 1.63 V with a satisfying stability performance.The exploitation and utilization of fossil fuels have leaded to environmental degradation and fossil energy depletion, [1][2][3][4] therefore, it is urgent to search for low-priced, cleaning, and renewable energy resources. Hydrogen energy is expected to substitute fossil energy due to its high calorific value and noncarbonaceous peculiarity. [5][6][7][8] Electrochemical water splitting contained simultaneous hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is regarded as one of the most significant routes for producing hydrogen, [9][10][11] but it is still limited by some factors. The dominant limitation is the large overpotential in water splitting process, therefore, efficient catalysts must be used to accelerate reaction rate and reduce overpotential. In conventional commercial production, Pt is the highest HER catalyst while RuO 2 is the optimal OER catalyst, nevertheless, the scarcity and costliness of those catalysts hinder their wide uses. [12,13] Accordingly, it is highly desired to develop efficient non-noble bifunctional catalysts for water splitting.Transition metal layered double hydroxides are considered to promising materials for OER to reduce the overpotential and promote electrolysis efficiency, [14][15][16][17][18] however, most of them have poor catalytic performance toward HER. As we all know, transition metal tetrathiomolybdate show remarkably efficient catalytic performance in HER. [19][20][21] For improving both HER and OER in water splitting, the coupling of HER and OER catalysts is significant. [22,23] Currently, many researches focus on combining the advantages of HER-and OER-efficient materials to construct core-shell structures, [24][25][26][27] increasing catalytic activity benefited from the large defect-rich at the hetero interface. Inspired by this, we expect to convert transition metal hydroxides at the surface into transition metal tetrathiomolybdate to achieve efficient performance of both HER and OER.Here, we demonstrate the ...

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Lattice Matching Growth of Conductive Hierarchical Porous MOF/LDH Heteronanotube Arrays for Highly Efficient Water Oxidation

et al. 2021

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The conjugation of metal–organic frameworks (MOFs) into different multicomponent materials to precisely construct aligned heterostructures is fascinating but elusive owing to the disparate interfacial energy and nucleation kinetics. Herein, a promising lattice‐matching growth strategy is demonstrated for conductive MOF/layered double hydroxide (cMOF/LDH) heteronanotube arrays with highly ordered hierarchical porous structures enabling an ultraefficient oxygen evolution reaction (OER). CoNiFe‐LDH nanowires are used as interior template to engineer an interface by inlaying cMOF and matching two crystal lattice systems, thus conducting a graft growth of cMOF/LDH heterostructures along the LDH nanowire. A class of hierarchical porous cMOF/LDH heteronanotube arrays is produced through continuously regulating the transformation degree. The synergistic effects of the cMOF and LDH components significantly promote the chemical and electronic structures of the heteronanotube arrays and their electroactive surface area. Optimized heteronanotube arrays exhibit extraordinary OER activity with ultralow overpotentials of 216 and 227 mV to deliver current densities of 50 and 100 mA cm−2 with a small Tafel slope of 34.1 mV dec−1, ranking it among the best MOF and non‐noble‐metal‐based catalysts for OER. The robust performance under high current density and vigorous gas bubble conditions enable such hierarchical MOF/LDH heteronanotube arrays as promising materials for practical water electrolysis.

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Ternary Ni-Co-Fe oxyhydroxide oxygen evolution catalysts: Intrinsic activity trends, electrical conductivity, and electronic band structure

Cited by 155 publications

References 71 publications

Oxygen Evolution on Metal‐oxy‐hydroxides: Beneficial Role of Mixing Fe, Co, Ni Explained via Bifunctional Edge/acceptor Route

Oxygen Evolution on Metal‐oxy‐hydroxides: Beneficial Role of Mixing Fe, Co, Ni Explained via Bifunctional Edge/acceptor Route

Synergy of Cobalt Iron Tetrathiomolybdate Coated on Cobalt Iron Carbonate Hydroxide Hydrate Nanowire Arrays for Overall Water Splitting

Lattice Matching Growth of Conductive Hierarchical Porous MOF/LDH Heteronanotube Arrays for Highly Efficient Water Oxidation

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