ACS Applied Materials & Interfaces
ACS Applied Materials & Interfaces
5 years ago

A Copper(II)-Paddlewheel Metal–Organic Framework with Exceptional Hydrolytic Stability and Selective Adsorption and Detection Ability of Aniline in Water

A Copper(II)-Paddlewheel Metal–Organic Framework with Exceptional Hydrolytic Stability and Selective Adsorption and Detection Ability of Aniline in Water
Yabo Xie, Lin-Hua Xie, Bin Wang, Xiaoqing Wang, Jinping Li, Jian-Rong Li, Ya Chen
Copper(II)-paddlewheel-based metal–organic frameworks (CP-MOFs) represent a unique subclass of MOFs with highly predictable porous structures, facile syntheses, and functional open metal sites. However, the lack of high hydrolytic stability is an obstacle for CP-MOFs in many practical applications. In this work, we report a new CP-MOF, [Cu4(tdhb)] (BUT-155), which is constructed from a judiciously designed carboxylate ligand with high coordination connectivity (octatopic), abundant hydrophobic substituents (six methyl groups), and substituent constrained geometry (tetrahedral backbone), tdhb8– [H8tdhb = 3,3′,5,5′-tetrakis(3,5-dicarboxyphenyl)-2,2′,4,4′,6,6′-hexamethylbiphenyl)]. BUT-155 shows high porosity with a Brunauer–Emmett–Teller surface area of 2070 m2/g. Quite interestingly, this CP-MOF retains its structural integrity after being treated in water for 10 days at room temperature or in boiling water for 24 h. To the best of our knowledge, BUT-155 represents the first CP-MOF that is demonstrated to retain its structural integrity in boiling water. The high hydrolytic stability of BUT-155 allowed us to carry out adsorption studies of water vapor and aqueous organic pollutants on it. Water-vapor adsorption reveals a sigmoidal isotherm and a high uptake (46.7 wt %), which is highly reversible and regenerable. In addition, because of the availability of soft-acid-type open Cu(II) sites, BUT-155 shows a high performance for selective adsorption of soft-base-type aniline over water or phenol, and a naked-eye detectable color change for the MOF sample accompanies this. The adsorption selectivity and high adsorption capacity of aniline in BUT-155 are also well-interpreted by single-crystal structures of the water- and aniline-included phases of BUT-155.

Publisher URL: http://dx.doi.org/10.1021/acsami.7b07920

DOI: 10.1021/acsami.7b07920

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