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High-Performance Ammonium Cobalt Phosphate Nanosheet Electrocatalyst for Alkaline Saline Water Oxidation.

ABSTRACT: The development of highly efficient electrocatalysts toward the oxygen evolution reaction is imperative for advancing water splitting technology to generate clean hydrogen energy. Herein, a two dimensional (2D) nanosheet ammonium cobalt phosphate hydrate (NH₄CoPO₄·H₂O) catalyst based on the earth-abundant non-noble metal is reported. When used for the challenging alkaline saline water electrolysis, the NH₄CoPO₄·H₂O catalyst with the optimal thickness of 30 nm achieves current densities of 10 and 100 mA cm^-2 at the record low overpotentials of 252 and 268 mV, respectively, while maintaining remarkable stability during the alkaline saline water oxidation at room temperature. X-ray absorption fine spectra reveal that the activation of Co (II) ions (in NH₄CoPO₄·H₂O) to Co (III) species constructs the electrocatalytic active sites. The 2D nanosheet morphology of NH₄CoPO₄·H₂O provides a larger active surface area and more surface-exposed active sites, which enable the nanosheet catalyst to facilitate the alkaline freshwater and simulated seawater oxidation with excellent activity. The facile and environmentally-benign H₂O-mediated synthesis route under mild condition makes NH₄CoPO₄·H₂O catalyst highly feasible for practical manufacturing. In comparison with noble metals, this novel electrocatalyst offers a cost-effective alternative for economic saline water oxidation to advance water electrolysis technology.

SUBMITTER: Song Z

PROVIDER: S-EPMC8292903 | biostudies-literature | 2021 Jul

REPOSITORIES: biostudies-literature

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High-Performance Ammonium Cobalt Phosphate Nanosheet Electrocatalyst for Alkaline Saline Water Oxidation.

Song Zhongxin Z Wang Kaixi Cathy KC Sun Qian Q Zhang Lei L Li Junjie J Li Dingjiu D Sze Pok-Wai PW Liang Yue Y Sun Xueliang X Fu Xian-Zhu XZ Luo Jing-Li JL

Advanced science (Weinheim, Baden-Wurttemberg, Germany) 20210516 14

The development of highly efficient electrocatalysts toward the oxygen evolution reaction is imperative for advancing water splitting technology to generate clean hydrogen energy. Herein, a two dimensional (2D) nanosheet ammonium cobalt phosphate hydrate (NH4CoPO4·H2O) catalyst based on the earth-abundant non-noble metal is reported. When used for the challenging alkaline saline water electrolysis, the NH4CoPO4·H2O catalyst with t ...[more]

PMID: 34306978

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Project description:The development of efficient and stable earth-abundant water oxidation catalysts is vital for economically feasible water-splitting systems. Cobalt phosphate (CoPi)-based catalysts belong to the relevant class of nonprecious electrocatalysts studied for the oxygen evolution reaction (OER). In this work, an in-depth investigation of the electrochemical activation of CoPi-based electrocatalysts by cyclic voltammetry (CV) is presented. Atomic layer deposition (ALD) is adopted because it enables the synthesis of CoPi films with cobalt-to-phosphorous ratios between 1.4 and 1.9. It is shown that the pristine chemical composition of the CoPi film strongly influences its OER activity in the early stages of the activation process as well as after prolonged exposure to the electrolyte. The best performing CoPi catalyst, displaying a current density of 3.9 mA cm-2 at 1.8 V versus reversible hydrogen electrode and a Tafel slope of 155 mV/dec at pH 8.0, is selected for an in-depth study of the evolution of its electrochemical properties, chemical composition, and electrochemical active surface area (ECSA) during the activation process. Upon the increase of the number of CV cycles, the OER performance increases, in parallel with the development of a noncatalytic wave in the CV scan, which points out to the reversible oxidation of Co2+ species to Co3+ species. X-ray photoelectron spectroscopy and Rutherford backscattering measurements indicate that phosphorous progressively leaches out the CoPi film bulk upon prolonged exposure to the electrolyte. In parallel, the ECSA of the films increases by up to a factor of 40, depending on the initial stoichiometry. The ECSA of the activated CoPi films shows a universal linear correlation with the OER activity for the whole range of CoPi chemical composition. It can be concluded that the adoption of ALD in CoPi-based electrocatalysis enables, next to the well-established control over film growth and properties, to disclose the mechanisms behind the CoPi electrocatalyst activation.

Dataset Information

High-Performance Ammonium Cobalt Phosphate Nanosheet Electrocatalyst for Alkaline Saline Water Oxidation.

Publications

High-Performance Ammonium Cobalt Phosphate Nanosheet Electrocatalyst for Alkaline Saline Water Oxidation.

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