Unlocking the performance of ternary metal (hydro)oxide amorphous catalysts <i>via</i> data-driven active-site engineering

Zhang, Doudou; Li, Haobo; Lu, Haijiao; Yin, Zongyou; Fusco, Zelio; Riaz, Asim; Reuter, Karsten; Catchpole, Kylie; Karuturi, Siva

doi:10.1039/d3ee01981k

Cited by 21 publications

(9 citation statements)

References 57 publications

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“…Electronic structure analysis is a necessary tool to excavate the origins of the reaction activity and provide insights into the nature of the active sites. Typically, band characteristics, , bonding characteristics, ,, and charge-transfer/spin polarization characteristics − are common electronic structure analysis methods for elucidating the intrinsic properties of active sites. The lattice N hydrogenation process and the adsorption configurations of intermediate species are just shown in Figure d.…”

Section: Resultsmentioning

confidence: 99%

Design Principle of Molybdenum-Based Metal Nitrides for Lattice Nitrogen-Mediated Ammonia Production

Qian,

Dai,

Feng

et al. 2024

JACS Au

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Chemical looping ammonia synthesis (CLAS) is a promising technology for reducing the high energy consumption of the conventional ammonia synthesis process. However, the comprehensive understanding of reaction mechanisms and rational design of novel nitrogen carriers has not been achieved due to the high complexity of catalyst structures and the unrevealed relationship between electronic structure and intrinsic activity. Herein, we propose a multistage strategy to establish the connection between catalyst intrinsic activity and microscopic electronic structure fingerprints using density functional theory computational energetics as bridges and apply it to the rational design of metal nitride catalysts for lattice nitrogen-mediated ammonia production. Molybdenum-based nitride catalysts with well-defined structures are employed as prototypes to elucidate the decoupled effects of electronic and geometrical features. The electron-transfer and spin polarization characteristics of the magnetic metals are constructed as descriptors to disclose the atomic-scale causes of intrinsic activity. Based on this design strategy, it is demonstrated that Ni 3 Mo 3 N catalysts possess the highest lattice nitrogen-mediated ammonia synthesis activity. This work reveals the structure−activity relationship of metal nitrides for CLAS and provides a multistage perspective on catalyst rational design.

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Section: Resultsmentioning

confidence: 99%

Design Principle of Molybdenum-Based Metal Nitrides for Lattice Nitrogen-Mediated Ammonia Production

Qian,

Dai,

Feng

et al. 2024

JACS Au

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“…In this regard, non-noble metal-based electrocatalysts (Co, Ni, Fe, etc. ), such as transition-metal dichalcogenides, metal oxides, metal hydroxides, etc., have attracted much attention due to their abundance, cost-effectiveness, and sustainability. , Furthermore, transition-metal-based electrocatalysts also provided remarkable stability, such as bifunctional bimetallic phosphide (Ni x Co y P) supported on nickel form (NF), highly active ternary metal (hydro)oxide (NiFeCo), self-supported Mo-doped dual phase phosphide heterostructure on nickel foam (NF), Co-doped TiO 2 brookite phase nanorods, etc . Recently, layered double hydroxides (LDHs) (i.e., tunable metal cations in the two-dimensional (2D) host layers with exchangeable anions and water molecules in the interlayer space) have attracted immense attention due to their morphologies, facile synthesis methodologies, and high electrocatalytic activity for OER. , In the earlier studies, Co-based LDHs demonstrated excellent OER performance; , however, the stability of these materials needs to be improved.…”

Section: Introductionmentioning

confidence: 99%

One-Pot Synthesis of CoFe-Nanomesh for Oxygen Evolution Reaction

Sharma,

Paul

2024

ACS Appl. Nano Mater.

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Iron-doped cobalt-based nanomeshes have been synthesized in a one-pot methodology. 2-Methyl imidazole (2-HMIM) acted as an etchant, while high valent iron increased the acidity of the solution and helped to synthesize ultrathin (thickness 1.9−2.0 nm) two-dimensional (2D)-nanomeshes having small uniform mesopores (3.8−4.0 nm) on the basal plane with high surface area and high pore volume. 20% iron-doped nanomesh material (Co 0.8 Fe 0.2 (OH) x ) revealed the best water oxidation reactivity, having an overpotential of 314 ± 3 mV, a mass activity of 413 ± 19 A/g, a turnover frequency (TOF) of 1.41 ± 0.04 s −1 , and a TOF EIS of 4.15 ± 0.04 s −1 . Electrochemical results suggested that the Co 0.8 Fe 0.2 (OH) x -nanomesh had a double-layer capacitance of 12.2 mF/cm 2 , corresponding to a roughness factor of 452, i.e., ion accessibility inside the nanomaterial was improved 452 times compared to the geometrical surface area of the electrode. This remarkable reactivity was due to (a) improved active sites for water oxidation at protruding edge sites and narrow mesopores on the basal planes of nanomeshes, (b) narrow mesopores on the basal planes ensured vertical ion penetration, vacant sites for water oxidation, and easy O 2 release from the material, and (c) electrochemical impedance spectroscopy results suggested that nanomesh formation ensured fast charge propagation inside the nanomaterial during the oxygen evolution reaction (OER) and fast charge transfer at the electrode/electrolyte interface.

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“…22−24 Metal hydroxides have been reportedly synthesized using this technique, delivering excellent OER performance on various substrate materials and sizes as (photo)electrodes. 22,25,26 However, metal hydroxides are generally lacklustre in HER due to their inherent lack of HER active sites and overall low conductivity. 27 In contrast, reduced metals and metal alloys such as Ni and NiMo are more HER-active, particularly in alkaline electrolytes.…”

Section: ■ Introductionmentioning

confidence: 99%

“…To address this pertinent issue, it is necessary to develop facile, scalable methods in earth-abundant electrocatalyst synthesis to ensure that electrodes of various sizes can be fabricated in a cost-effective manner. One such promising approach is the solution-corrosion technique, done by corroding a metal substrate in a metal precursor solution at mild temperature conditions to create a desirable catalyst composition on the surface. − Metal hydroxides have been reportedly synthesized using this technique, delivering excellent OER performance on various substrate materials and sizes as (photo)electrodes. ,, However, metal hydroxides are generally lacklustre in HER due to their inherent lack of HER active sites and overall low conductivity . In contrast, reduced metals and metal alloys such as Ni and NiMo are more HER-active, particularly in alkaline electrolytes …”

Section: Introductionmentioning

confidence: 99%

Enhancing the Hydrogen Evolution Reaction Performance of Solution-Corroded NiMo via Plasma Modification

Soo,

Riaz,

Zhang

et al. 2024

Chem. Mater.

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In pursuit of efficient water-splitting technologies, the development of high-performing electrocatalysts is crucial, particularly for the hydrogen evolution reaction (HER). In addition, it is paramount to adopt cost-effective approaches that leverage earth-abundant metals, together with scalable synthesis methods. In this study, we introduce a synthesis approach that combines a facile solution corrosion technique with plasma modification, thereby enhancing the hydrogen evolution activity of NiMo alloys. The inclusion of NH3 plasma modification plays a dual role by concurrently reducing and nitriding as-synthesized NiMo hydroxide. The treatment results in a significant reduction in the HER overpotential to 95 mV at 10 mA/cm2 compared to its initial overpotential. This improvement is attributed to enhanced kinetics due to substantial reductions in charge transfer resistance and an increased double-layer capacitance. Furthermore, the catalyst demonstrates excellent stability of close to 120 h, thereby highlighting the potential of this synthesis method for large-area synthesis of HER electrocatalysts.

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Unlocking the performance of ternary metal (hydro)oxide amorphous catalysts via data-driven active-site engineering

Abstract: A machine-learning methodology was applied to unveil the structure–property relationships of the fabricated ternary Ni, Fe, and Co amorphous oxygen evolution catalyst, showcasing remarkable performance and stability via corrosion engineering.

Cited by 21 publications

References 57 publications

Design Principle of Molybdenum-Based Metal Nitrides for Lattice Nitrogen-Mediated Ammonia Production

Design Principle of Molybdenum-Based Metal Nitrides for Lattice Nitrogen-Mediated Ammonia Production

One-Pot Synthesis of CoFe-Nanomesh for Oxygen Evolution Reaction

Enhancing the Hydrogen Evolution Reaction Performance of Solution-Corroded NiMo via Plasma Modification

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