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Metal–organic frameworks are recognized as a new generation of emerging porous materials in a variety of applications including adsorption and photocatalysis. The present study presents the development of ternary composite materials made through the coupling of UiO-66 with palygorskite (Pal) clay mineral and titanium dioxide (TiO2) applied as adsorbent and photocatalyst for the removal of methyl orange (MO) from aqueous solutions as a typical anionic dye. The prepared materials were characterized using XRD, ATR, DR UV/Vis, and TGA analysis. Detailed kinetic experiments revealed that the presence of the clay at low amounts in the composite outperformed the adsorption efficiency of pure UiO-66, increasing MO adsorption by ca. 8%. In addition, coupling Pal/UiO-66 with TiO2 for the production of ternary composites provided photocatalytic properties that resulted in complete removal of MO. This was not observed in the pure UiO-66, the Pal/UiO-66 composite, or the pure TiO2 material. This study presents the first example of clay mineral/MOF/TiO2 composites with improved performance in removing dyes from aqueous solutions and highlights the importance of coupling MOFs with low-cost clay minerals and photocatalysts for the development of multifunctional advanced composites.

Herein, a novel composite material containing UiO-66 and palygorskite (Pal) clay mineral was prepared using a facile one-pot synthesis process. The material was studied using a variety of techniques and applied as did not affect the structure of the metal-organic framework (MOF) part, but induced a small increase in specific surface area. The developed Pal/UiO-66 composite presented excellent adsorption efficiency against MO removal, as evidenced by detailed kinetic and isotherm experiments. An impressive maximum adsorption capacity at equilibrium was evidenced; 340 mg g−1 at pH = 5 and T = 25 °C. This corresponds to a 34.5 % increase compared with pure UiO-66, considering only the MOF content. Furthermore, the Pal/UiO-66 composite was proven stable and highly recyclable, losing less than 9% of the removal capacity after five consecutive cycles. The study highlights the synergistic effect of the coupling of MOF structures with low-cost and abundant clay minerals for the development of advanced absorbents.