Amazon raw clay as a precursor of a clay-based adsorbent: experimental study and DFT analysis for the adsorption of Basic Yellow 2 dye

Abstract

A clay-based adsorbent (CBA) was purified from a sustainable precursor (raw clay, RC), which was obtained from the Amazon region in Brazil. The CBA was characterized using X-ray diffraction (XRD), Fourier Transform Infrared spectroscopy (FTIR), Brunauer-Emmet-Teller surface area (S_BET, RC = 23.386 m².g^-1, CBA = 33.020 m².g^-1), Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDS), thermogravimetric analysis (TGA), cation exchange capacity (CEC, CBA = 44.75 cmol/kg), and point of zero charge analyses (pH_PZC, CBA = 2.20). Subsequently, CBA was used to adsorb basic yellow 2 (BY2) dye from aqueous solutions. A CBA dosage (1 g/L), initial concentration of dye (C₀ = 15 mg/L), and pH (5.6) were ideal conditions for the BY2 dye removal of ~ 98%. The BY2 kinetics was better represented by the pseudo-first-order (PFO) model while the BY2 equilibrium was well represented by the Sips model, with a maximum adsorption capacity of q_ms = 18.04 mg/g at 28 °C. The negative values of ΔG° and ΔH° showed that the studied process is spontaneous and exothermic, while the values of isosteric heat (∆H_st, -16 to -20 kJ/mol) suggest a predominance of physical interactions. The molecular chemical reactivity of BY2 was investigated using quantum chemical descriptors calculated based on Density Functional Theory (DFT) optimization of the dye molecule, and the results revealed a large energy gap value (4.3900 eV) and considerable chemical hardness (η = 2.1950 eV). Therefore, the correlation between DFT and experimental results consistently sustains that BY2 dye tends to be adsorbed on the CBA surface by electrostatic interactions, thus, this is the possible adsorption mechanism of this process.

Keywords: Adsorption; Auramine-o; Chemical water pollutants; Clays; DFT calculations; Water decolorization.