Synthesis and Application of Thiourea-Poly(Acrylic Acid)-Formaldehyde Composites for Removal of Crystal Violet Dye

硫脲-聚丙烯酸-甲醛复合材料的合成及其在去除结晶紫染料中的应用

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Abstract

Textile dye effluents, particularly cationic dyes, pose a major environmental challenge, demanding efficient and sustainable adsorbent materials to remove harmful synthetic dyes. In this study, a reference thiourea-formaldehyde (TU/FA) composite and a series of thiourea-poly(acrylic acid)-formaldehyde (TU/PAA/FA) composites were synthesized and systematically characterized. The composites were prepared by varying the volume of poly(acrylic acid) PAA (from 1 to 7.5 mL) to assess how PAA incorporation influences morphology, crystallinity, surface chemistry, charge, and thermal stability. Analytical techniques including SEM, XRD, FT-IR, particle size distribution, zeta potential, and TGA/DTG revealed that increasing PAA content induced more porous and amorphous microstructures, intensified carbonyl absorption, reduced particle size (optimal at 2.5-5 mL PAA), and shifted the zeta potential from near-neutral to highly negative values (-37 to -41 mV). From TU/PAA/FA composite analysis, it was depicted that the TU/PAA-5/FA material has the better characteristics as a potential cationic dye absorbent. Thus, the adsorption performance of this composite toward crystal violet dye was subsequently investigated and compared to the reference material thiourea-formaldehyde (TU/FA). The TU/PAA-5/FA material exhibited the highest capacity (145 mg/g), nearly twice that of TU/FA (74 mg/g), due to the higher density of carboxylic groups facilitating electrostatic attraction. Adsorption was pH-dependent, maximized at pH 6, and decreased with temperature, confirming an exothermic process. Kinetic data followed a pseudo-second-order model (R(2) = 0.99), implying chemisorption as the rate-limiting step, while Langmuir isotherms (R(2) > 0.97) indicated monolayer adsorption. Thermodynamic analysis (ΔH° < 0, ΔS° < 0, ΔG° > 0) further supported an exothermic, non-spontaneous mechanism. Overall, the TU/PAA-5/FA composite combines enhanced structural stability with high adsorption efficiency, highlighting its potential as a promising, low-cost material for the removal of cationic dyes from textile effluents.

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