Sensor Absorbents for Heavy Metal Ions By Low-Cost Functionalization of Porous Carbons

Abstract

Porous carbons are key materials in electrodes for electrochemical energy storage as well as in water purification. Methods to modify porous carbons to enhance their properties as charge storing or water purification materials have been explored during the past decades [1,2]. The main application fields if porous carbon, water purification and energy storage, are highly cost sensitive. For this reason, there is a need to develop low-cost methods to modify porous carbons. Here, the use of benzoxazine chemistry to modify porous carbons is explored. Benzoxazine chemistry can be considered a protection group strategy for phenols, where the phenols from which the benzoxazines are synthesized, are deprotected upon benzoxazine polymerization. Further, benzoxazine polymerization produces Mannich bridges located near phenol groups, motifs that can be used to capture heavy metal ions. More specifically, in the first step, the porous carbons are partially impregnated with benzoxazine monomers, from melt or solutions to afford powders impregnated far below the liquid saturation level of the particles. That is, the particles retain porosity after the impregnation but still have a dry appearance. After impregnation, the particles are heated over the polymerization temperature of the benzoxazine to afford the porous carbon with immobilized functionalities. As phenols can initiate benzoxazine polymerization and be incorporated in the polymer, this method offers a simple route to produce polymerized and immobilized structure at a carbon interface. Here, results on metal ion absorption and the electrochemical response after exposure are presented for carbons modified by impregnation-polymerization of benzoxazines with or without incorporation of phenols. Inks were manufactured from the modified carbons. The electrochemical characterizations were performed on printed arrays of electrochemical cells on a substrate having dimensions of well plates and intended for automatized testing and where the carbon inks were deposited on the working electrodes. This methodology has a potential of simplifying the development of sensor materials and absorbents and can be automatized and potentially be supported with machine learning schemes. The electrochemical responses of exposure of the modified carbon electrodes to metal salt solutions show that impregnation-polymerization of functional benzoxazine can produce absorbents responding electrochemically to metal ion absorption with a scalable process starting from low-cost materials.