Coordination Unsaturation and Basic Site-Immobilized Nanochannel in a Chemorobust MOF for 3-Fold-Increased High-Temperature Selectivity and Fixation of CO 2 under Mild Conditions with Nanomolar Recognition of Roxarsone.

A multifaceted metal-organic framework (MOF) with task-specific site-engineered pores can promise high-temperature and moisture-tolerant capture and non-redox fixation of CO 2 under mild conditions as well as ultrasensitive detection of carcinogenic contaminants in water. Herein, we report a pillar-bilayered MOF that holds a nanochannel with contrasting functionalities for both these sustainable applications with improved performance characteristics. The twofold entangled robust framework exhibits CO 2 adsorption at elevated temperatures with considerable MOF-gas interaction. Interestingly, CO 2 selectivity unveils nearly a 3-fold improvement upon the rise of temperature, affording a CO 2 /N 2 value of 820 at 313 K, which outperforms many porous adsorbents. Additionally, breakthrough simulation establishes complete separation and attests the potential of this MOF in the separation of flue gas mixture. Importantly, minor CO 2 loss during multiple capture-release cycles and under a relative humidity of 75% promise practical usability of the material. Density functional theory (DFT) not only portrays the atomistic level snapshots of temperature-triggered CO 2 inclusion inside this microporous vessel alongside the role of diverse CO 2 -philic sites but also validates the basis of N 2 -phobicity of an azo-functionalized linker on such increased selectivity. The guest-free MOF further demonstrates non-redox and recyclable CO 2 fixation with wide epoxide tolerance under solvent-free mild conditions and even works at atmospheric pressure and room temperature. The crucial roles of high-density acid-base sites in both adsorption and catalysis are supported by control experiments and by comparing the activity of an unfunctionalized MOF. The hydrolytic stability and strong luminescence signature benefit the framework in aqueous-phase selective and fast responsive detection of detrimental roxarsone (ROX) with high quenching (7.56 × 10 4 M -1 ) and very low sensitivity (68 nM). Apart from varying degrees of an energy-transfer mechanism, the fluorosensing of ROX is comprehensively supported by in-depth DFT studies that manifest alteration of MOF energy levels in the presence of organoarsenic compounds and depict MOF-analyte supramolecular interactions.