The design of artificial receptors with a specific recognition function and enhanced selectivity is highly desirable in the electrochemical sensing field, which can be used for detection of environmental pollutants. In this facet, metal–organic frameworks (MOFs) featured adjustable porosities and specific host-guest recognition properties. Especially, the large hydrophobic cavity formed in the porous MOFs may become a potential artificial receptor. We herein designed a new porous MOF [Zn2(L)­(IPA)­(H2O)]·2DMF·2MeOH·3H2O (Zn-L-IPA) by using a functionalized sulfonylcalix[4]­arene (L 1 ) and isophthalic acid (H2IPA) (DMF = N,N′-dimethylformamide). The specific pore size and pore shape of Zn-L-IPA made it efficiently selective for absorption of bisphenol A (BPA), bisphenol F (BPF), and bisphenol S (BPS). Therefore, a rapid, highly selective, and ultrasensitive electrochemical sensing platform Zn-L-IPA@GP/GCE was fabricated by using Zn-L-IPA as a host to recognize and absorb bisphenol guests (GP = graphite powder, GCE = glassy carbon electrode). Most strikingly, the extremely low detection limits were up to 3.46 and 0.17 nM for BPA and BPF, respectively, using the Zn-L-IPA@GP/GCE electrode. Furthermore, the “recognition and adsorption” mechanism was uncovered by density functional theory with the B3LYP function. This work offered a prospective strategy for selective absorption and detection of harmful bisphenols with the MOF-based porous material.

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