Processes associated with ionic current rectification at a 2D-titanate nanosheet deposit on a microhole poly(ethylene terephthalate) substrate

Films of titanate nanosheets (approx. 1.8-nm layer thickness and 200-nm size) having a lamellar structure can form electrolyte-filled semi-permeable channels containing tetrabutylammonium cations. By evaporation of a colloidal solution, persistent deposits are readily formed with approx. 10-μm thickness on a 6-μm-thick poly(ethylene-terephthalate) (PET) substrate with a 20-μm diameter microhole. When immersed in aqueous solution, the titanate nanosheets exhibit a p.z.c. of − 37 mV, consistent with the formation of a cation conducting (semi-permeable) deposit. With a sufficiently low ionic strength in the aqueous electrolyte, ionic current rectification is observed (cationic diode behaviour). Currents can be dissected into (i) electrolyte cation transport, (ii) electrolyte anion transport and (iii) water heterolysis causing additional proton transport. For all types of electrolyte cations, a water heterolysis mechanism is observed. For Ca²⁺ and Mg²⁺ions, water heterolysis causes ion current blocking, presumably due to localised hydroxide-induced precipitation processes. Aqueous NBu₄⁺ is shown to ‘invert’ the diode effect (from cationic to anionic diode). Potential for applications in desalination and/or ion sensing are discussed.

     

Decolourisation of reactive black-5 at an RVC substrate decorated with PbO2/TiO2 nanosheets prepared by anodic electrodeposition

Reticulated vitreous carbon (RVC) substrates were coated with a composite of PbO₂ and titanate nanosheets (TiNS) by anodic electrophoretic depostion. The structure and morphological characteristics of the coating were evaluated by field emission scanning electron microscopy (FESEM) and Raman spectroscopy. The TiNS/PbO₂/RVC coating contained the anatase phase and showed a well-defined, microporous morphology with hydrophilic character along the length and thickness of the RVC struts. Electrochemical and photocatalytic activity of the coatings facilitated RB-5 dye degradation as a model organic pollutant in wastewater. The electrochemical decolourisation involves the generation of hydroxyl free radicals over the TiNS/PbO₂/RVC anode composite surface, whereas photocatalytic decolourisation was driven by the synergetic photocatalytic effect imparted by the photoinduced holes and free electron acceptors. The photocatalytic properties of the TiNS/PbO₂ coating were achieved by calcination at 450 °C for 60 min in air which converted the titanate phase to anatase and modified its surface area. This enabled 98% electrochemical decolourisation of the RB-5 dye solution (measured by visible absorption at 597 nm) in a time of 60 min.

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