Environmentally superior cleaning of diatom frustules using sono-Fenton process: Facile fabrication of nanoporous silica with homogeneous morphology and controlled size

Existing techniques for the preparation of silica structures from diatom cells include cleaning of frustules through baking at high temperature and oxidant cleaning using concentrated sulfuric acid, hydrogen peroxide, nitric acid, or sodium dodecyl sulfate (SDS)/ethylenediaminetetraacetic acid (EDTA). In this study, sono-Fenton (SF) process was examined to prepare nanoporous silica through cleaning diatom frustules, while preserving their structural features. Single colonies of Cyclotella sp. were cultivated in batch mode f/2-enriched seawater. Combination of Fenton process with ultrasonication was found to be more efficient than the sum of individual processes in the removal of organic compounds from Cyclotella sp. structure. The optimized amounts of operational parameters were determined as suspension pH of 3, diatom cell density of 4.8 × 10⁵ cell mL⁻¹, H₂O₂ concentration of 60 mM, Fe²⁺ concentration of 15 mM, ultrasound irradiation power of 400 W and the temperature of 45 °C. The results of energy-dispersive X-ray spectroscopy (EDX) and thermal gravimetry (TG) analyses proved that organic materials covering the cell wall were significantly removed from the frustules through SF process. Scanning electron microscopy (SEM) images showed that after SF treatment, silica nanostructures were produced having uniform pores less than 15 nm in diameter. N₂ adsorption–desorption isotherms demonstrated that almost non-porous structure of diatom frustules became mesoporous during removing the organic matrix. Lipids, amino acids, carbohydrates and organic acids or their oxidized products were identified using GC–MS analysis as the main organic compounds released from diatom cells to the solution after SF treatment. Treated frustules exhibited adsorption capability of 91.2 mg/g for Methylene Blue, which was almost 2.5 times higher than that of untreated frustules (34.8 mg/g).