Efficient and precise recovery of phenol from coal chemical wastewater (CCW) poses a significant challenge, prompting the development of a novel aldehyde-based, ester-based hyper-cross-linked polar resin (DES–COOC–CHO) in this study. Two distinct functional group modification methods were employed to enhance the screening effect of the resin. SEM, FT-IR, NMR, XPS, and BET characterizations confirmed the successful construction of the hyper-cross-linked polar resin, incorporation aldehyde and ester groups, exhibiting a special surface area of 627.2 m2/g and a microporous specific surface area percentage of 29.94%. DES–COOC–CHO adhered to the pseudo-second-order kinetic model and Langmuir model (maximum adsorption capacity of 118.0 mg/g). Its adsorption of phenol was spontaneous chemisorption, monolayer adsorption. Notably, even after undergoing 20 adsorption–desorption cycles, the resin maintained a stable adsorption capacity, showcasing excellent recoverability. In the presence of phenols sharing similar properties, DES–COOC–CHO exhibited superior selectivity for phenol. In real CCW, it achieved a remarkable 90% selective removal rate of phenol. The primary selective mechanism relied on the hydrogen bonding effect facilitated by aldehyde and ester groups, coupled with microporous sieving of appropriate size. In comparison with other adsorbent materials, DES–COOC–CHO exhibited superior adsorption properties, coupled with a cost-effective preparation process, presenting significant potential for practical applications.
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