New insights on microscopic properties of metal-porphyrin complexes attached to quartz crystal sensor

A quartz crystal adsorbent coated with 5,10,15,20-tetrakis(4-methylphenyl) porphyrin was used to examine the complexation phenomenon of three metallic ions [aluminum(III), iron(III) and indium(III)]. The aim is to select the appropriate adsorbate for metalloporphyrin fabrication. The equilibrium adsorption isotherms of tetrakis(4-methylphenyl) porphyrin were performed at four temperatures (from 300 to 330 K) through the quartz crystal microbalance (QCM) method. Subsequently, the experimental data were analyzed in order to develop a thorough explanation of the complexation mechanisms. The experimental results indicated that the aluminum(III) chloride is the adequate material for metalloporphyrin application. Theoretical investigation was established through physics adsorption models in order to analyze the experimental isotherms. The AlCl₃ isotherms were modeled via a single-layer adsorption model which is developed using the ideal gas law. Whereas, the FeCl₃ isotherms were interpreted via a single-layer adsorption which includes the lateral interactions parameters (real gas law), indicating the lowest stability of the formed iron-porphyrin complex. The participation of the chloride ions in the double-layers adsorption of InCl₃ was interpreted via layer by layer formulation. Interestingly, the physicochemical investigation of the three adopted models indicated that the tetrakis(4-methylphenyl) porphyrin adsorption was an endothermic process and that the aluminum(III) chloride can be recommended for an industrial application because it presents the highest adsorption energy (chemical bonds with porphyrins).