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<p>This paper describes for the first time the response surface methodology (RSM) optimized conditions, isotherm, kinetics, thermodynamic studies for the optimum removal of methylene blue (MB) dye onto a 4,4-biphenyldicarboxylic acid (BPDC)-based zinc metal–organic framework (Zn-MOF) synthesized through the solvent-free mechanochemical route using a mortar and pestle, generating a high percentage yield of 73.45%. The as-prepared Zn-MOF was extensively characterized using FTIR, XRD, BET, EDXRF, SEM, TGA, and point of zero charge (pHpzc = 6), depicting formation of the framework, its stability, and suitable surface properties. Response surface methodology based on a Box–Behnken design was utilized to optimize the adsorption process. The optimum conditions were obtained at an adsorbent dosage of 0.422&#xa0;g, ionic strength of 0.0347&#xa0;mol/L, contact time of 61.78&#xa0;min, and pH 11.2, giving a predicted MB percentage removal of 99.51%, which closely align with the experimental value of 99.35% obtained. Isotherm analysis indicated that adsorption was controlled by adsorbate–adsorbent interactions on a heterogeneous surface and Temkin model gave the closest fit with R<sup>2</sup> value of 0.8828. In contrast, the Langmuir and Freundlich models had worse fits with lower R<sup>2</sup> values. Kinetic investigations further showed that the adsorption process followed a pseudo-second-order model. Thermodynamic parameters verified that the removal process was endothermic (ΔH° = 20.026&#xa0;kJ&#xa0;mol<sup>−1</sup>), spontaneous (ΔG° =  − 12.465 to − 17.396&#xa0;kJ&#xa0;mol<sup>−1</sup>), and entropy-driven (ΔS° =  + 112.638&#xa0;J&#xa0;mol<sup>−1</sup>&#xa0;K<sup>−1</sup>). The outcomes show that Zn-MOF produced mechanochemically is an efficient dye removal agent for aqueous systems.</p>

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Response surface methodology optimization of methylene blue dye removal using a mechanochemically synthesized zinc-based metal organic framework with its isotherm, kinetic and thermodynamic insights

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年8月5日

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  • Kamaluddeen Suleiman Kabo,
  • Olaniran Kolawole Akeremale,
  • Ikechukwu Ogadimma Alisi

摘要

This paper describes for the first time the response surface methodology (RSM) optimized conditions, isotherm, kinetics, thermodynamic studies for the optimum removal of methylene blue (MB) dye onto a 4,4-biphenyldicarboxylic acid (BPDC)-based zinc metal–organic framework (Zn-MOF) synthesized through the solvent-free mechanochemical route using a mortar and pestle, generating a high percentage yield of 73.45%. The as-prepared Zn-MOF was extensively characterized using FTIR, XRD, BET, EDXRF, SEM, TGA, and point of zero charge (pHpzc = 6), depicting formation of the framework, its stability, and suitable surface properties. Response surface methodology based on a Box–Behnken design was utilized to optimize the adsorption process. The optimum conditions were obtained at an adsorbent dosage of 0.422 g, ionic strength of 0.0347 mol/L, contact time of 61.78 min, and pH 11.2, giving a predicted MB percentage removal of 99.51%, which closely align with the experimental value of 99.35% obtained. Isotherm analysis indicated that adsorption was controlled by adsorbate–adsorbent interactions on a heterogeneous surface and Temkin model gave the closest fit with R2 value of 0.8828. In contrast, the Langmuir and Freundlich models had worse fits with lower R2 values. Kinetic investigations further showed that the adsorption process followed a pseudo-second-order model. Thermodynamic parameters verified that the removal process was endothermic (ΔH° = 20.026 kJ mol−1), spontaneous (ΔG° =  − 12.465 to − 17.396 kJ mol−1), and entropy-driven (ΔS° =  + 112.638 J mol−1 K−1). The outcomes show that Zn-MOF produced mechanochemically is an efficient dye removal agent for aqueous systems.