Adsorptive Separation of Aromatic Compounds from Alkanes by π-π Interactions in a Carbazole-Based Conjugated Microporous Polymer.

Separation of aromatic/alkane mixtures of similar size and properties is critical for the chemical industry as conventional thermal separation is a high-cost and an energy-intensive process. Adsorptive separation based on porous materials is a prospective and economical technology as well as a suitable alternative to the energy-inefficient heat-driven separation process. With this in mind, we design and synthesize a novel microporous polymer (termed CMP-S-1) with a conjugated aromatic skeleton as a porous adsorbent for aromatic/alkane separation. CMP-S-1 possesses high aromatic adsorption selectivity in two representative separation systems (benzene vs cyclohexane and 3-methylthiophene vs -octane) based on a vapor adsorption experiment and an ideal adsorbed solution theory simulation. The instant adsorption rate, adsorption energy calculations, and liquid fixed-bed breakthrough experiments give convincing demonstrations on the preferential selective adsorption of aromatic compounds over alkanes in CMP-S-1. The strong π-π interaction between aromatics and the naphthalene ring is considered as the main reason for the strong affinity of aromatic compounds in the CMP-S-1 skeleton. The remarkable aromatic/alkane separation performance of CMP-S-1 verifies the important influence of the π-conjugation interaction in the conjugated porous polymer for the low-energy consumption adsorption separation process.