RESUMEN
A novel doubly interpenetrated indium-organic framework of 1 has been assembled by In3+ ions and highly conjugated biquinoline carboxylate-based bitopic connectors (H2L). The isolated 1 exhibits an anionic framework possessing channel-type apertures repleted with exposed quinoline N atoms and carboxyl O atoms. Owing to the unique architecture, 1 displays a durable photoluminescence effect and fluorescence quenching sensing toward CrO42-, Cr2O72-, and Cu2+ ions with reliable selectivity and anti-interference properties, fairly high detection sensitivity, and rather low detection limits. Ligand-to-ligand charge transition (LLCT) was identified as the essential cause of luminescence by modeling the ground state and excited states of 1 using DFT and TD-DFT. In addition, the negatively charged framework has the ability to rapidly capture single cationic MB, BR14, or BY24 and their mixture, including the talent to trap MB from the (MB + MO) system with high selectivity. Moreover, intrinsic light absorption capacity and band structure feature endow 1 with effective photocatalytic decomposition ability toward reactive dyes RR2 and RB13 under ultraviolet light. Notably, after further polishing the band structure state of 1 by constructing the S-scheme heterojunction of In2S3/1, highly efficient photocatalytic detoxification of Cr(VI) and degradation of reactive dyes have been fully achieved under visible light. This finding may open a new avenue for designing novel multifunctional MOF-based platforms to address some intractable environmental issues, i.e., detection of heavy metal ions, physical capture of pony-sized dyes, and photochemical decontamination of ultrastubborn reactive dyes and highly toxic Cr(VI) ions from water.
RESUMEN
How to accurately detect and efficiently sweep Cr(VI) from contaminated water has come into focus. Zirconium-based metal-organic frameworks (MOFs) play vital roles in water environmental chemistry due to excellent hydrolysis-resistant stability. However, as photochemical probes and photocatalysts, poor performances in detection sensitivity, selectivity, and photosensitiveness limit sole Zr-MOFs' applications. So, it is urgent to quest valid strategies to break through the dilemmas. Embedding luminous dyes into MOFs has been considered one of the most feasible avenues. Herein, a dual-emissive RhB@Zr-MOF with orange-yellow fluorescence has been assembled by in situ-encapsulating rhodamine B (RhB) into a zirconium-biquinoline-based MOF. Actually, within RhB@Zr-MOF, the aggregation fluorescence quenching (ACQ) effect of RhB molecules was effectively avoided. Notably, RhB@Zr-MOF exhibits a rapid fluorescence quenching response toward Cr(VI) ions with high selectivity, sensitivity, and anti-interference abilities. More interestingly, unlike the most widely reported fluorescence resonance energy transfer (FRET) between MOFs and encapsulated guest modules, photoinduced electron transfer from RhB to Zr-MOF has been confirmed by modeling the ground state and excited states of RhB@Zr-MOF using density functional theory (DFT) and time-dependent DFT (TD-DFT). The effective electron transfer makes RhB@Zr-MOF more sensitive in probing Cr2O72- and CrO42- ions with ultralow detection limit (DL) values of 6.27 and 5.26 ppb, respectively. Prominently, the detection sensitivity based on DL values has been increased about 6 and 9 times, respectively, compared with pristine Zr-MOF. Moreover, rather negative CB and positive VB potentials make RhB@Zr-MOF have excellent photochemical scavenging ability toward Cr(VI) and MO.