Correction to “From NiMoO4 to γ-NiOOH: Detecting the Active Catalyst Phase by Time Resolved in Situ and Operando Raman Spectroscopy”

In an effort to support the large-scale implementation of clean hydrogen in industry and society, the electrolytic decomposition of water is considered a realistically enticing prospect, provided the guarantee of affordable and durable material components. Within alkaline systems, earth-abundant electrocatalysts could provide both these requirements. However, a continued exploration of the reactivity and the causes behind different behaviors in performance are necessary to guide optimization and design. In this paper, Ta-doped NiO thin films are prepared via DC magnetron sputtering (1–2–4 at % Ta) to demonstrate the effect of surface electronic modulation by non-3d elements on the catalysis of the oxygen evolution reaction (OER). Material properties of the catalysts are analyzed via Rutherford backscattering spectrometry, X-ray diffractometry, photoelectron spectroscopy, and Raman spectroscopy. Ta impurities are shown to be directly responsible for increasing the valence state of Ni sites and enhancing reaction kinetics, resulting in performance improvements of up to 64 mV at 10 mA cm –2 relative to pristine NiO. Particularly, we show that by applying operando Raman spectroscopy, Ta enhances the ability to create high-valence Ni in γ-NiOOH at a lower overpotential compared to the undoped sample. The lowered overpotentials of the OER can thus be attributed to the energetically less hindered advent of the creation of γ-NiOOH species on the pre-catalyst surface: a phenomenon otherwise unresolved through simple voltammetry.

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Nickel Site Modification by High-Valence Doping: Effect of Tantalum Impurities on the Alkaline Water Electro-Oxidation by NiO Probed by Operando Raman Spectroscopy

Saguì

Ström

Edvinsson

et al. 2022

ACS Catal.

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Oxygen-Plasma-Induced Hetero-Interface NiFe2O4/NiMoO4 Catalyst for Enhanced Electrochemical Oxygen Evolution

Wei

et al. 2022

Materials

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The electrolysis of water to produce hydrogen is an effective method for solving the rapid consumption of fossil fuel resources and the problem of global warming. The key to its success is to design an oxygen evolution reaction (OER) electrocatalyst with efficient conversion and reliable stability. Interface engineering is one of the most effective approaches for adjusting local electronic configurations. Adding other metal elements is also an effective way to enrich active sites and improve catalytic activity. Herein, high-valence iron in a heterogeneous interface of NiFe2O4/NiMoO4 composite was obtained through oxygen plasma to achieve excellent electrocatalytic activity and stability. In particular, 270 mV of overpotential is required to reach a current density of 50 mA cm−2, and the overpotential required to reach 500 mA cm−2 is only 309 mV. The electron transfer effect for high-valence iron was determined by X-ray photoelectron spectroscopy (XPS). The fast and irreversible reconstruction and the true active species in the catalytic process were identified by in situ Raman, ex situ XPS, and ex situ transmission electron microscopy (TEM) measurements. This work provides a feasible design guideline to modify electronic structures, promote a metal to an active oxidation state, and thus develop an electrocatalyst with enhanced OER performance.

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Correction to “From NiMoO₄ to γ-NiOOH: Detecting the Active Catalyst Phase by Time Resolved in Situ and Operando Raman Spectroscopy”

Cited by 2 publications

References 3 publications

Nickel Site Modification by High-Valence Doping: Effect of Tantalum Impurities on the Alkaline Water Electro-Oxidation by NiO Probed by Operando Raman Spectroscopy

Nickel Site Modification by High-Valence Doping: Effect of Tantalum Impurities on the Alkaline Water Electro-Oxidation by NiO Probed by Operando Raman Spectroscopy

Oxygen-Plasma-Induced Hetero-Interface NiFe2O4/NiMoO4 Catalyst for Enhanced Electrochemical Oxygen Evolution

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