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Investigation of the structural and electrical conductivity properties in pure and cation exchanged rectorite
Abstract Clay minerals, as biofriendly and low-cost materials, are highly essential for the modern industrial applications including the production of clean energy, its storage and conversion. Here, the capabilities of pure and cation exchanged rectorite, a regularly interstratified phyllosilicate from Beatrix Mine (South Africa) were explored and discussed. A comprehensive characterization was performed by means of high resolution solid-state NMR, electrochemical impedance spectroscopy and powder X-ray diffraction. 23Na MAS and 3QMAS NMR spectroscopy was used to characterize accessibility of interlayer space in rectorite for exchangeable cations. Three Na sites attributed to easily exchangeable Na+ on the surface or in large pores, Na+ in dehydrated micaceous interlayers and Na+ in hydrated smectite interlayers were identified. Differences in hydration states in smectitic interlayers depending on the type of intercalation were detected using 1H MAS NMR. A higher amount of hydrating water molecules in pure and Mg-exchanged rectorites was attributed to the higher hydration energy of Ca2+ and Mg2+. The temperature dependences of electrical conductivity in this work were best described using the empirical Vogel-Tammann-Fulcher equation with the temperature-dependent effective activation energy parameter. Significantly stronger change of activation energy in Mg2+ exchanged rectorite in the temperature range of 10 °C to 50 °C as compared to pure rectorite and its Na+, Li+ and NH4 + modifications was related to an extensive H-bond network in the interlayers, which facilitated an effective proton transfer responsible for electric conductivity. The obtained resutls suggested a greater potential for the use of Mg-exchanged rectorite as ionic conductor at enhanced temperatures.
Graphical abstract Display Omitted
Highlights Rectorite from Beatrix Mine was studied towards the structure – conducting properties relation. Accessibility of interlayer space for exchangeable cations was characterized by solid state NMR. Electrical conductivity in rectorite depends on interlayer cations, hydration and temperature. Conductivity originates from proton transfer over the hydrating water network in the interlayers. Mg-exchanged rectorite has a great potential as ionic conductor at enhanced temperatures.
Investigation of the structural and electrical conductivity properties in pure and cation exchanged rectorite
Abstract Clay minerals, as biofriendly and low-cost materials, are highly essential for the modern industrial applications including the production of clean energy, its storage and conversion. Here, the capabilities of pure and cation exchanged rectorite, a regularly interstratified phyllosilicate from Beatrix Mine (South Africa) were explored and discussed. A comprehensive characterization was performed by means of high resolution solid-state NMR, electrochemical impedance spectroscopy and powder X-ray diffraction. 23Na MAS and 3QMAS NMR spectroscopy was used to characterize accessibility of interlayer space in rectorite for exchangeable cations. Three Na sites attributed to easily exchangeable Na+ on the surface or in large pores, Na+ in dehydrated micaceous interlayers and Na+ in hydrated smectite interlayers were identified. Differences in hydration states in smectitic interlayers depending on the type of intercalation were detected using 1H MAS NMR. A higher amount of hydrating water molecules in pure and Mg-exchanged rectorites was attributed to the higher hydration energy of Ca2+ and Mg2+. The temperature dependences of electrical conductivity in this work were best described using the empirical Vogel-Tammann-Fulcher equation with the temperature-dependent effective activation energy parameter. Significantly stronger change of activation energy in Mg2+ exchanged rectorite in the temperature range of 10 °C to 50 °C as compared to pure rectorite and its Na+, Li+ and NH4 + modifications was related to an extensive H-bond network in the interlayers, which facilitated an effective proton transfer responsible for electric conductivity. The obtained resutls suggested a greater potential for the use of Mg-exchanged rectorite as ionic conductor at enhanced temperatures.
Graphical abstract Display Omitted
Highlights Rectorite from Beatrix Mine was studied towards the structure – conducting properties relation. Accessibility of interlayer space for exchangeable cations was characterized by solid state NMR. Electrical conductivity in rectorite depends on interlayer cations, hydration and temperature. Conductivity originates from proton transfer over the hydrating water network in the interlayers. Mg-exchanged rectorite has a great potential as ionic conductor at enhanced temperatures.
Investigation of the structural and electrical conductivity properties in pure and cation exchanged rectorite
Vyalikh, Anastasia (author) / Atanasova, Maria T. (author) / Focke, Walter W. (author) / Makarova, Anna A. (author) / Krajnc, Andraz (author) / Mali, Gregor (author)
Applied Clay Science ; 245
2023-08-27
Article (Journal)
Electronic Resource
English
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