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Effect of Intercalants inside Birnessite-Type Manganese Oxide Nanosheets for Sensor Applications

  • Phatsawit Wuamprakhon
    Phatsawit Wuamprakhon
    Centre of Excellence for Energy Storage Technology (CEST), Department of Chemical and Biomolecular Engineering, School of Energy Science and Engineering, Vidyasirimedhi Institute of Science and Technology, Rayong 21210, Thailand
  • Atiweena Krittayavathananon
    Atiweena Krittayavathananon
    Centre of Excellence for Energy Storage Technology (CEST), Department of Chemical and Biomolecular Engineering, School of Energy Science and Engineering, Vidyasirimedhi Institute of Science and Technology, Rayong 21210, Thailand
  • Soracha Kosasang
    Soracha Kosasang
    Centre of Excellence for Energy Storage Technology (CEST), Department of Chemical and Biomolecular Engineering, School of Energy Science and Engineering, Vidyasirimedhi Institute of Science and Technology, Rayong 21210, Thailand
  • Nattapol Ma
    Nattapol Ma
    Centre of Excellence for Energy Storage Technology (CEST), Department of Chemical and Biomolecular Engineering, School of Energy Science and Engineering, Vidyasirimedhi Institute of Science and Technology, Rayong 21210, Thailand
    More by Nattapol Ma
  • Thana Maihom
    Thana Maihom
    Centre of Excellence for Energy Storage Technology (CEST), Department of Chemical and Biomolecular Engineering, School of Energy Science and Engineering, Vidyasirimedhi Institute of Science and Technology, Rayong 21210, Thailand
    Department of Chemistry, Faculty of Liberal Arts and Science, Kasetsart University, Kamphaeng Saen Campus, Nakhon Pathom 73140, Thailand
    More by Thana Maihom
  • Jumras Limtrakul
    Jumras Limtrakul
    Centre of Excellence for Energy Storage Technology (CEST), Department of Chemical and Biomolecular Engineering, School of Energy Science and Engineering, Vidyasirimedhi Institute of Science and Technology, Rayong 21210, Thailand
  • Narong Chanlec
    Narong Chanlec
    Synchrotron Light Research Institute (Public Organization), 111 University Avenue, Muang District, Nakhon Ratchasima 30000, Thailand
  • Pinit Kidkhunthod
    Pinit Kidkhunthod
    Synchrotron Light Research Institute (Public Organization), 111 University Avenue, Muang District, Nakhon Ratchasima 30000, Thailand
  • , and 
  • Montree Sawangphruk*
    Montree Sawangphruk
    Centre of Excellence for Energy Storage Technology (CEST), Department of Chemical and Biomolecular Engineering, School of Energy Science and Engineering, Vidyasirimedhi Institute of Science and Technology, Rayong 21210, Thailand
    *Email: [email protected]
Cite this: Inorg. Chem. 2020, 59, 21, 15595–15605
Publication Date (Web):August 20, 2020
https://doi.org/10.1021/acs.inorgchem.0c01592
Copyright © 2020 American Chemical Society

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    Abstract

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    Hydrazine is a common reducing agent widely used in many industrial and chemical applications; however, its high toxicity causes severe human diseases even at low concentrations. To detect traces of hydrazine released into the environment, a robust sensor with high sensitivity and accuracy is required. An electrochemical sensor is favored for hydrazine detection owing to its ability to detect a small amount of hydrazine without derivatization. Here, we have investigated the electrocatalytic activity of layered birnessite manganese oxides (MnO2) with different intercalants (Li+, Na+, and K+) as the sensor for hydrazine detection. The birnessite MnO2 with Li+ as an intercalant (Li-Bir) displays a lower oxidation peak potential, indicating a catalytic activity higher than the activities of others. The standard heterogeneous electron transfer rate constant of hydrazine oxidation at the Li-Bir electrode is 1.09- and 1.17-fold faster than those at the Na-Bir and K-Bir electrodes, respectively. In addition, the number of electron transfers increases in the following order: K-Bir (0.11 mol) < Na-Bir (0.17 mol) < Li-Bir (0.55 mol). On the basis of the density functional theory calculation, the Li-Bir sensor can strongly stabilize the hydrazine molecule with a large adsorption energy (−0.92 eV), leading to high electrocatalytic activity. Li-Bir also shows the best hydrazine detection performance with the lowest limit of detection of 129 nM at a signal-to-noise ratio of ∼3 and a linear range of 0.007–10 mM at a finely tuned rotation speed of 2000 rpm. Additionally, the Li-Bir sensor exhibits excellent sensitivity, which can be used to detect traces of hydrazine without any effect of interference at high concentrations and in real aqueous-based samples, demonstrating its practical sensing applications.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c01592.

    • Results of FE-SEM, FTIR, Raman spectroscopy, cyclic voltammetry, in situ XAS, and chronoamperometry, diffusion coefficients, and a comparison of sensor performance with those of previous works (PDF)

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    Cited By

    This article is cited by 3 publications.

    1. Hitomi Yano, Akihisa Aimi, Nobuyuki Sakai, Takayoshi Sasaki, Kenjiro Fujimoto. Single-Crystal Growth of Layered Birnessite-Type Manganese Oxides and Their Delamination into MnO2 Nanosheets. Crystal Growth & Design 2022, 22 (1) , 625-632. https://doi.org/10.1021/acs.cgd.1c01171
    2. Robert D. Crapnell, Craig E. Banks. Electroanalytical overview: the electroanalytical sensing of hydrazine. Sensors & Diagnostics 2022, 1 (1) , 71-86. https://doi.org/10.1039/D1SD00006C
    3. Juan Xie, Haizhu Yang, Xinqiang Wang, Feng Gao. ZIF-8/electro-reduced graphene oxide nanocomposite for highly electrocatalytic oxidation of hydrazine in industrial wastewater. Microchemical Journal 2021, 168 , 106521. https://doi.org/10.1016/j.microc.2021.106521

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