Enabling and Inducing Oxygen Vacancies in Cobalt Iron Layer Double Hydroxide via Selenization as Precatalysts for Electrocatalytic Hydrogen and Oxygen Evolution Reactions

  • Arun Karmakar
    Arun Karmakar
    Academy of Scientific and Innovative Research (AcSIR), Ghaziabad 201002, India
    Electrochemical Process Engineering (EPE) Division, CSIR-Central Electrochemical Research Institute (CECRI), Karaikudi 630003, Tamil Nadu, India
  • Kannimuthu Karthick
    Kannimuthu Karthick
    Academy of Scientific and Innovative Research (AcSIR), Ghaziabad 201002, India
    Electrochemical Process Engineering (EPE) Division, CSIR-Central Electrochemical Research Institute (CECRI), Karaikudi 630003, Tamil Nadu, India
  • Sangeetha Kumaravel
    Sangeetha Kumaravel
    Academy of Scientific and Innovative Research (AcSIR), Ghaziabad 201002, India
    Electrochemical Process Engineering (EPE) Division, CSIR-Central Electrochemical Research Institute (CECRI), Karaikudi 630003, Tamil Nadu, India
  • Selvasundarasekar Sam Sankar
    Selvasundarasekar Sam Sankar
    Academy of Scientific and Innovative Research (AcSIR), Ghaziabad 201002, India
    Electrochemical Process Engineering (EPE) Division, CSIR-Central Electrochemical Research Institute (CECRI), Karaikudi 630003, Tamil Nadu, India
  • , and 
  • Subrata Kundu*
    Subrata Kundu
    Academy of Scientific and Innovative Research (AcSIR), Ghaziabad 201002, India
    Electrochemical Process Engineering (EPE) Division, CSIR-Central Electrochemical Research Institute (CECRI), Karaikudi 630003, Tamil Nadu, India
    *Email: [email protected], [email protected]. Tel/Fax: (+91) 4565-241487.
Cite this: Inorg. Chem. 2021, 60, 3, 2023–2036
Publication Date (Web):January 22, 2021
https://doi.org/10.1021/acs.inorgchem.0c03514
Copyright © 2021 American Chemical Society
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Abstract

Production of hydrogen by water electrolysis is an environment-friendly method and comparatively greener than other methods of hydrogen production such as stream reforming carbon, hydrolysis of metal hydride, etc. However, sluggish kinetics of the individual half-cell reactions hinders the large-scale production of hydrogen. To minimize this disadvantage, finding an appropriate, competent, and low-cost catalyst has attracted attention worldwide. Layer double hydroxide (LDH)-based materials are promising candidates for oxygen evolution reaction (OER) but not fruitful and their hydrogen evolution reaction (HER) activity is very poor, due to the lack of ionic conductivity. The inclusion of chalcogenide and generation of inherent oxygen vacancies in the lattice of LDH lead to improvement of both OER and HER activities. The presence of rich oxygen vacancies was confirmed using both the Tauc plot (1.11 eV, vacancy induction) and the photoluminescence study (peak at 426 nm, photoregeneration of oxygen). In this work, we have developed vacancy-enriched, selenized CoFe-LDH by the consequent wet-chemical and hydrothermal routes, respectively, which was used for OER and HER applications in 1 M KOH and 0.5 M H2SO4 electrolytes, respectively. For OER, the catalyst required only 251 mV overpotential to reach a 50 mA/cm2 current density with a Tafel slope value of 47 mV/dec. For HER, the catalyst demanded only 222 mV overpotential for reaching a 50 mA/cm2 current density with a Tafel slope value of 126 mV/dec. Hence, generating oxygen vacancies leads to several advantages from enhancing the exposed active sites to high probability in obtaining electrocatalytically active species and subsequent assistance in oxygen and hydrogen molecule cleavage.

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  • Methods of synthesis; electrode fabrication; material preparation for different characterizations; data for OER; HER studies; and comparative electrocatalysis data (PDF)

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