Devising Chemically Robust and Cationic Ni(II)-MOF with Nitrogen-Rich Micropores for Moisture Tolerant CO Capture: Highly Regenerative and Ultra-Fast Colorimetric Sensor for TNP and Multiple Oxo-Anions in Water with Theoretical Revelation.

08:00 EDT 4th October 2019 | BioPortfolio

Summary of "Devising Chemically Robust and Cationic Ni(II)-MOF with Nitrogen-Rich Micropores for Moisture Tolerant CO Capture: Highly Regenerative and Ultra-Fast Colorimetric Sensor for TNP and Multiple Oxo-Anions in Water with Theoretical Revelation."

Metal-organic frameworks (MOFs) show distinctive superiority for carbon dioxide (CO) capture and luminescent sensing of toxic pollutants over other materials, where combination of both these properties together with improvement of hydrolytic stability and pore functionality is critical to environmental remediation applications. The Ni(II)-framework, [Ni(µ-OH)()()](NO)⋅6DMA⋅6MeOH () ( = 4,4',4''-(1H-imidazole-2,4,5-triyl)tripyridine, H = azobenzene-4,4'-dicarboxylic acid, DMA = Dimethylacetamide, CSMCRI = Central Salt & Marine Chemicals Research Institute), encompassing cationic [Ni(μ-OH)(CO)] SBUs, is solvothermally synthesized from nitrogen-rich and highly fluorescent organic struts. The non-interpenetrated structure, containing free nitrogen atom affixed microporous channels, is stable in organic solvents, and weakly basic and acidic aqueous solutions. The activated MOF () exhibits strong CO-framework interaction, and extremely selective CO adsorption over N (292.5) and CH (11.7). Importantly, water vapour exposure does not affect the surface area and/or multiple CO uptake-release cycles, signifying potential of the porous structure for long-term use under humid conditions. Aqueous phase sensing studies illustrate extremely specific and ultra-fast detection of explosive 2,4,6-trinitrophenol (TNP) via remarkable fluorescence quenching (K = 1.3×10 M), with 0.25 ppm limit of detection (LOD). Furthermore, serves as unique luminescent probe for highly discriminative and quick responsive detection of three noxious oxo-anions (CrO, CrO, MnO) in water via noteworthy turn-off responses, and extreme low LODs (Cr
0.9; Cr
0.29; Mn
0.25 ppm). It is imperative to stress the outstanding reusability of the MOF towards multicyclic sensing of all four major water contaminants, alongside visible colorimetric changes upon individual analyte detection. Mechanistic insights in light of electron transfer route, together with density functional theory calculations portrays the influence of pore functionalization in framework-analyte interactions, including alternation in energy levels, where varying degree of contribution of energy transfer explicitly authenticates high quenching of the material.


Journal Details

This article was published in the following journal.

Name: ACS applied materials & interfaces
ISSN: 1944-8252


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