Adsorption Behaviors and Mechanisms of Methyl Orange on Heat-Treated Palygorskite Clays

Understanding completely the interaction of clay mineral and anionic dye is very important for the applications of clay minerals. In this paper, the adsorption behaviors of heat-treated palygorskite clays for methyl orange (MO) from an aqueous medium were studied using equilibrium batch and theoretic calculation techniques. The crystal structure and surface appearance of the heat-treated samples were studied using Fourier transform infrared (FTIR) and scanning electron microscopy (SEM). The adsorption results reveal that a higher calcining temperature helps in improving removal performance of palygorskite clay for methyl orange. The isothermal adsorption experiments show that there is almost no adsorption at low dye concentrations but a sudden linear increase occurs when the dye concentration exceeds to a certain value. A lower change point is observed for 700 °C treated sample compared with that of the natural sample. The leaching of exchangeable Mg²⁺ ions located in palygorskite should be a key factor affecting the adsorption capacity. Both the experimental and theoretical studies suggest that the adsorption of MO onto heat-treated palygorskite clay is controlled by the two mechanisms: for samples treated at lower temperatures (<300 °C), the hydrogen bonding between oxygen groups of −SO₃^– (anionic head groups of MO) and H⁺ of both the bound zeolitic water and coordinated water should be important. While for samples calcined at higher temperature (>400 °C), electrostatic interaction between the dye–Mg²⁺ complexes and negatively charged surface of heat-treated palygorskite clay becomes dominant. In addition, the latter becomes stronger with the increasing the calcination temperature, which can be ascribed to the formation of a higher ratio of complexes and stronger negatively charged surface of the adsorbent caused by leaching of more metal ions. This work provides a deep insight into the interaction of heat-treated palygorskite clay and anionic dye, which paves the way for their practical applications in anionic dye adsorption.