Site Energy Distribution Coupled with Statistical Physics Modeling for Cr(VI) Adsorption onto Coordination Polymer Gel

In this work, a novel pristine coordination polymer gel composed of zirconium and 2-amino-5-mercapto-1,3,4-thiadiazole is unveiled and explored to remove Cr(VI) from aqueous systems. A Box–Behnken design, coupled with a genetic algorithm and desirability function, was used for optimizing the controllable factors for maximum removal efficiency. Under optimized conditions (A = 50 mg L –1, B = 40 mg, C = 90 min, and D = 4), 99% of Cr(VI) was removed, and the saturation adsorption capacity recorded was 132.37 mg g –1 . The adsorption data were investigated through statistical physics modeling. The most suited statistical physics model (monolayer with three energies; R 2 = 0.994–0.997, χ 2 = 0.008–0.024), combined with site energy distribution analysis, XPS, and FTIR, unraveled the uptake mechanism. At the first and third active sites, Cr(VI) uptake was multimolecular ( n > 1), while at the second active site, it was a mixed multimolecular (298 K, n > 1) and multidocking (308 and 318 K, n < 1). The adsorption energy values indicated the involvement of coordination exchange ( E 1 = 53.40–58.47 kJ mol –1 ), electrostatic interaction ( E 2 = 29.56–32.29 kJ mol –1 ), and hydrogen bonding ( E 3 = 24.68–28.35 kJ mol –1 ) in Cr(VI) adsorption. The BSf(1.5, α) model fitted best ( R 2 = 0.976–0.994, χ 2 = 0.023–0.377) to the kinetic data under all conditions. Common coexisting ions had no significant impact on removal efficiency (% R > 97% at 1:3), and the sorbent could be reutilized up to 5 uptake-elution cycles (>96% efficiency). The practical utility of ZrAMTD was investigated by remediating Cr(VI) contaminated real water samples (% R ≥ 92.91%).