Premium
Engineered Bifunctional Luminescent Pillared‐Layer Frameworks for Adsorption of CO 2 and Sensitive Detection of Nitrobenzene in Aqueous Media
Author(s) -
Su ChunHao,
Tsai MengJung,
Wang WeiKai,
Li YiYun,
Wu JingYun
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202005373
Subject(s) - nitrobenzene , bifunctional , adsorption , microporous material , aqueous solution , metal organic framework , chemistry , sorption , luminescence , quenching (fluorescence) , ligand (biochemistry) , inorganic chemistry , fluorescence , crystallography , materials science , organic chemistry , catalysis , biochemistry , physics , receptor , optoelectronics , quantum mechanics
Through a dual‐ligand synthetic approach, five isoreticular primitive cubic (pcu)‐type pillared‐layer metal–organic frameworks (MOFs), [Zn 2 (dicarboxylate) 2 (NI‐bpy‐44)] ⋅ x DMF ⋅ y H 2 O, in which dicarboxylate=1,4‐bdc ( 1 ), Br‐1,4‐bdc ( 2 ), NH 2 ‐1,4‐bdc ( 3 ), 2,6‐ndc ( 4 ), and bpdc ( 5 ), have been engineered. MOFs 1 – 5 feature twofold degrees of interpenetration and have open pores of 27.0, 33.6, 36.8, 52.5, and 62.1 %, respectively. Nitrogen adsorption isotherms of activated MOFs 1′ – 5′ at 77 K all displayed type I adsorption behavior, suggesting their microporous nature. Although 1′ and 3′ – 5′ exhibited type I adsorption isotherms of CO 2 at 195 K, MOF 2′ showed a two‐step gate‐opening sorption isotherm of CO 2 . Furthermore, MOF 3′ also had a significant influence of amine functions on CO 2 uptake at high temperature due to the CO 2 –framework interactions. MOFs 1 – 5 revealed solvent‐dependent fluorescence properties; their strong blue‐light emissions in aqueous suspensions were efficiently quenched by trace amounts of nitrobenzene (NB), with limits of detection of 4.54, 5.73, 1.88, 2.30, and 2.26 μ m , respectively, and Stern–Volmer quenching constants ( K sv ) of 2.93×10 3 , 1.79×10 3 , 3.78×10 3 , 4.04×10 3 , and 3.21×10 3 m −1 , respectively. Of particular note, the NB‐included framework, NB@ 3 , provided direct evidence of the binding sites, which showed strong host–guest π–π and hydrogen‐bonding interactions beneficial for donor–acceptor electron transfer and resulting in fluorescence quenching.