Fabrication of two dual-functionalized covalent organic polymers through heterostructural mixed linkers and their use as cationic dye adsorbents

With the rapid development of industrialization, population growth and long-term droughts, the scarcity of clean water and increasing environmental pollution are becoming critical issues. Porous organic polymer materials have been proposed as good candidates for removing pollutant compounds from water supplies. However, because of their finite synthetic chemical reactions and monotonous building blocks, fabricating covalent organic polymer materials with multiple linkages and various different multi-functional components remains a huge challenge. Herein, two dual-functionalized covalent organic polymers (JLUE-COP-1 and JLUE-COP-2) were prepared through heterostructural mixed linkers via imine and hydrazone linkages based on Schiff base condensation. Possessing the advantages of porosity and π-conjugated phenyl rings, as well as functional –CO–NH– and –SO(3)H building units, the resultant dual-functionalized JLUE-COPs exhibited high capabilities for the removal of the cationic dye methylene blue (MB). Experiments were carried out to investigate the effects of pH, dye concentration, contact time and temperature on the performance of the JLUE-COPs. The kinetics, equilibrium properties, thermodynamics and mechanisms were studied. It was found that the adsorption processes of the two JLUE-COPs both followed the second-order kinetic model and can be described well by the Langmuir model. Notably, the differences in the surface and pore volumes of the two JLUE-COPs lead to differences in the adsorption rate, adsorption efficiency and maximum adsorption capacity. In addition, activation energy values and some thermodynamic parameters such as ΔG(Θ), ΔH(Θ) and ΔS(Θ) suggest that the adsorption processes of dyes onto the JLUE-COPs are entropy-driven, endothermic and spontaneous. Our work thus paves the way for developing functionalized COPs as a new type of platform for removing cationic dyes from wastewater.