Innovative eco-friendly methyl orange removal: Mechanism, kinetic, and thermodynamic study using starch cryogel-integrated mesoporous silica nanoparticles

Abstract

This study introduces a novel, eco−friendly composite, uncalcined mesoporous silica nanoparticles incorporated into a starch cryogel (MSNs-Cry), designed for the effective removal of methyl orange (MO) from water. MSNs−Cry integrates uncalcined mesoporous silica nanoparticles (MSNs) within a starch cryogel network, leveraging the high adsorption capacity of MSNs. The composite achieved a maximum adsorption capacity of 18.98 mg g⁻1 and demonstrated high removal efficiencies of 99.00 % ± 0.21 % in synthetic water (10 mg L−1 MO) and 92.77 % ± 1.76 % in real wastewater containing 0.43 mg L−1 MO. The Langmuir isotherm model provided a superior fit (R2 = 0.9930) compared to the Freundlich model (R2 = 0.9180), and the adsorption kinetics followed a pseudo−second−order model (R2 = 0.9917). The primary adsorption mechanisms included electrostatic attraction, hydrophobic interactions, and hydrogen bonding. The process was endothermic (ΔH° = 31.3 kJ mol−1), spontaneous, and more favorable at higher temperatures (ΔG° = −34.2 to −38.6 kJ mol−1 at 298–318 K). In the presence of sodium silicate at 13.1 times the MO concentration, removal efficiency drops by 35.77 %, and with sodium sulfate and urea at 100 times the MO concentration, it decreases by 8.65 %. Despite these challenges, MSNs−Cry effectively removes MO in the presence of the anionic dye Congo Red and metal ions, demonstrating its selective adsorption capabilities. The tablet form of MSNs−Cry prevents the loss of uncalcined MSNs, mitigating potential environmental and operational impacts. Additionally, the composite's effectiveness at a natural pH of 6.65 eliminates the need for pH adjustment, offering a cost−effective solution for real−world applications. This study establishes MSNs−Cry as a promising material for sustainable water purification.