Lanthanide Metal-organic Frameworks Research Articles

Luminescent Trade-Off Effect Arising from Y3+ Ion Doping in Rare Earth Metal–Organic Framework Solid Solutions Tb1-Xyx-Ptc (H3ptc = Pyridine-2, 4, 6-Tricarboxylate)

Luminescent Trade-Off Effect Arising from Y3+ Ion Doping in Rare Earth Metal–Organic Framework Solid Solutions Tb1-Xyx-Ptc (H3ptc = Pyridine-2, 4, 6-Tricarboxylate)

Rational synthesis of isomorphic rare earth metal–organic framework materials for simultaneous adsorption and photocatalytic degradation of organic dyes in water

Two isomorphic rare earth metal–organic frameworks (MOFs) were synthesized by a solvothermal method. These MOFs have good removal effects on cationic and neutral dyes through simultaneous adsorption and photocatalysis.

A 2-in-1 multi-functional sensor for efficient epinephrine detection based on a cucurbit[7]uril functionalized lanthanide metal–organic framework and its intelligent application in a molecular robot

The immediate identification of disease analytes in the human body requires a facile sensing method with high reliability and selectivity.

Stable lanthanide metal–organic frameworks as ratiometric fluorescent probes for the efficient detection of riboflavin

A stable Ln-MOF architecture with tunable luminescence properties has been successfully prepared, showing excellent performance towards the fluorescence detection of riboflavin.

Calix[6]arene functionalized lanthanide metal-organic frameworks with boosted performance in identifying an anti-epidemic pharmaceutical.

A novel composite was fabricated by hybridizing terbium 1,3,5-benzenetricarboxylic MOF (TB-MOF) with Cx[6]. The obtained composite TB-Cx[6] possessed long-term stability and dispersion stability and was used for on-site analysis of the anti-COVID-19 disinfection product Prednis via a combing remote sampling technique.

A series of isostructural lanthanide metal–organic frameworks: effective fluorescence sensing for Fe3+, 2,4-DNP and 4-NP

A series of isostructural lanthanide metal–organic frameworks were constructed under solvothermal conditions. Among them, JLU-MOF201-Y and JLU-MOF201-Tb display high sensitivity and selectivity for Fe3+, 2,4-dinitrophenol and 4-hydroxyderricin.

Introducing lanthanide metal–organic framework and perovskite onto pulp fibers for fluorescent anti-counterfeiting and encryption

Introducing lanthanide metal–organic framework and perovskite onto pulp fibers for fluorescent anti-counterfeiting and encryption

Hybrid composites of lanthanide metal-organic frameworks with epoxy silanes for highly sensitive thermometry.

Post-synthetic modification of metal-organic frameworks (MOFs) and fabrication of hybrid composites are currently hot topics in the development of new functional materials. In this study, a facile and direct approach for coupling of lanthanide MOFs with epoxy silanes was developed, providing an access to a new series of functional composites. Two types of commercially available epoxy silane, namely 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ECTMS) and (3-glycidoxypropyl)methyl diethoxysilane (KH563), were used to modify Ln-BTB MOFs ([Ln(BTB)(H2O)]n·2n(C6H12O); Ln = Tb or Eu0.001Tb0.999; H3BTB = 1,3,5-benzenetrisbenzoic acid) via covalent grafting involving mechanical grinding, epoxide coupling and curing reactions. The fabricated composites (Tb-BTB@ECTMS, Eu0.001Tb0.999-BTB@ECTMS, Tb-BTB@KH563, Eu0.001Tb0.999-BTB@KH563) and their Ln-MOF precursors were fully characterized, including a detailed study of their stability and fluorescence properties. The obtained composites show high thermal and solution stability, under boiling water conditions and in a wide pH range of 1-12. Application of the composites as temperature sensors in the 197-297 K and 273-343 K temperature ranges was explored in detail, revealing a remarkable sensing behavior. For example, Tb-BTB@ECTMS shows a maximum relative sensitivity (Sr) of 6.85% K-1 at 343 K. Eu0.001Tb0.999-BTB@ECTMS represents a white-light emission material with the CIE coordinates (0.3194, 0.3049) that are very close to those of white light, along with good temperature sensing performance and a relative sensitivity of 4.32% K-1 at 297 K. An enhanced performance of the composites in comparison with the parent MOF materials as well as the mechanism of energy transfer were rationalized by DFT calculations. By unveiling a facile and efficient method for improving the stability of luminescent MOFs, via post-synthetic grafting with epoxy silanes, the present study will stimulate further research at the interface of materials chemistry, MOF design, photoluminescence and temperature sensing.

Data-driven efficient synthetic exploration of anionic lanthanide-based metal-organic frameworks.

The synthesis of lanthanide metal-organic frameworks with terephthalate (Ln-BDC-MOFs) was investigated using a data-driven approach. Visually mapping the previously reported synthetic conditions suggested the existence of unexplored search spaces for novel Ln-BDC-MOFs. By focusing on the unexplored chemical reaction space, we successfully synthesized a series of new anionic Ln-BDC-MOFs, KGF-15, which demonstrated potential as luminescent sensors for Cu2+ ions. This synthetic exploration approach can significantly reduce the experimental effort required to discover new materials.

Fluorescent Lanthanide Metal-Organic Framework for Rapid and Ultrasensitive Detection of Methcathinone in Human Urine

Fluorescent Lanthanide Metal-Organic Framework for Rapid and Ultrasensitive Detection of Methcathinone in Human Urine

In situ optical spectroscopy for monitoring plasma-assisted formation of lanthanide metal-organic frameworks.

A novel system was designed, which integrated in situ spectral monitoring with facile synthesis of lanthanide metal-organic frameworks in dielectric barrier discharge (DBD) plasma. It features miniaturization, cost-effectiveness and universality, for in situ spectral information of scattering and luminescence to gain insight into the reactive processes.

An electrochemically deposited ordered hierarchical metal–organic framework-based dual-module sensor for decoding organic vapors

A dual-module lanthanide MOF film with three-dimensional ordered macro-microporous structure was fabricated to discriminate six amines, enabling a multi-analyte recognition decoding scheme.

A cationic fcu-lanthanide MOF enhances the uptake of iodine vapour at room temperature

The first example of a cationic cluster-based fcu-lanthanide metal-organic framework (MOF) bearing an asymmetric linker, herein named UOTT-4, has been designed and fully characterized. Compared to its rare-earth (RE) anionic counterpart (RE-UiO-66), UOTT-4 was found to significantly improve the performance towards adsorption of iodine vapour at room temperature, opening avenues for the design of the next-generation cationic porous materials for the beneficial uptake and confinement of target molecules.

Multifunctional lanthanide MOF luminescent sensor built by structural designing and energy level regulation of a ligand

In order to reduce usage cost and simplify the detection process, it is necessary to develop multifunctional and multi-emitter Ln-MOF luminescent sensors.

White light emission phosphor modulation, nitrobenzene sensing property and barcode anti-counterfeiting via lanthanides post-functionalized metal-organic frameworks

Three isostructural lanthanide metal-organic frameworks (Ln-MOFs) [Ln2(L)3(H2O)5]n (1-Ln, Ln ​= ​Eu, Tb, Dy and Eu/Tb), and a transition MOF {[Cd(L)(H2O)2]·H2O}n (1-Cd) based on 1-(4-carboxyphenyl)-1H-pyrazole-3-carboxylic acid (H2L) ligand were obtained by solvothermal method. The white-light-emitting (WLE) material Eu3+/Tb3+@1-Cd with the CIE coordinate (0.33, 0.34) was successfully modulated by introducing Eu3+ and Tb3+ into the blue-emitting 1-Cd. The post-synthetic doping provides a facile and practical strategy for the development of WLE materials. Besides, the luminescence sensing experiments showed that 1-Ln can be used as an excellent probe for nitrobenzene detecting. And the multi-color barcode of 1-Ln showed great potential in commodity anti-counterfeiting and information security.

Ratiometric fluorescence and chromaticity dual-readout assay for β-glucuronidase activity based on luminescent lanthanide metal-organic framework

β-Glucuronidase (GCU) is a biomarker of many malignant tumors. The accurate and sensitive detection of GCU is of significance for the early diagnosis of diseases. Herein, we proposed a ratiometric fluorescence/chromaticity dual-readout assay method for GCU activity by integrating a luminescent lanthanide metal-organic framework (MOF) and fluorescence turn-on enzymolysis reaction. MOF-253 synthesized by Al3+ and 2,2′-bipyridine-5,5′-dicarboxylic acid was used as scaffold to prepare Eu3+@MOF-253 with red emission, which plays multiple roles in GCU assay including fluorescence internal standard, synergistic enzyme catalysis and chromaticity shift enhancement. 4-Methylumbelliferyl-β-glucuronide was selected as substrate and hydrolyzed by GCU to produce 4-methylumbelliferyl with blue emission, which can quench the fluorescence of Eu3+@MOF-253 due to internal filter effect. Therefore, the turn-on/off ratiometric fluorescence assay method of GCU was established, and it exhibits a wide linear range of 0.1–50 U L−1, low limit of detection (LOD) of 0.03 U L−1 and good selective response. Furthermore, a portable device with illuminometer as RGB signal readout was designed to perform the ratiometric chromaticity visual assay of GCU, which has the linear range of 0.2–40 U L−1 and the LOD of 0.06 U L−1. The dual-readout method was applied to detect GCU in human serum and shows high accuracy and precision (recovery of 92.4–114.1%, relative standard deviation < 7.9%). Both the ratiometric fluorescence and the ratiometric chromaticity assay get the same results as the classical colorimetric assay. To our knowledge, this is the first report on the ratiometric fluorescence/chromaticity dual-readout assay of GCU activity.

A luminescent lanthanide MOF as highly selective and sensitive fluorescent probe for nitrobenzene and Fe3+

A lanthanide metal-organic framework, {[Tb(FDA)1.5(DMF)]·DMF}n (Tb-FDA) was designed and prepared by mixing Tb3+ and 2,5-furandicarboxylic acid (H2FDA) under solvothermal condition. The crystal structure of the complex was determined by single-crystal X-ray diffraction. The thermal stability and the luminescence properties of Tb-FDA were studied. The detection of organic molecules and cations and the interference of other analytes were considered and investigated in detail, revealing the excellent performance of Tb-FDA for sensing nitrobenzene (NB) and Fe3+ with high efficiency, sensitivity and chemical stability. In addition, the sensing function possesses selectivity even with the existence of other analogous interfering substances. The mechanism of fluorescence quenching with NB and Fe3+ was also given in this work.

A Terbium‐Based MOF as fluorescent probe for the detection of Malachite Green, Fe3+ and MnO4−

AbstractLanthanide MOFs (Ln‐MOFs) have been widely used in biological imaging and fluorescence detection due to their remarkable optical advantages and variable structural designability. We prepared a terbium‐based metal‐organic framework (Tb‐TDA) and applied to the research of fluorescence detection. The detection result demonstrated that Tb‐TDA can efficiently recognize malachite green (MG), Fe3+ and MnO4− by fluorescent quenching, having high quenching efficiency Ksv (7.02×104 M−1 for MG; 1.06×104 M−1 for Fe3+; 1.59×104 M−1 for MnO4−) and low detection limit (MG: 0.0765 μM; Fe3+: 0.697 μM; MnO4−: 0.612 μM). The quenching of Tb‐TDA's fluorescence emission by MG, Fe3+ and MnO4− was likely due to the spectral overlap, energy transfer and competition. Among seven analytes, 13 metal cations and 13 anions, Tb‐TDA can fast and effectively recognize MG, Fe3+ and MnO4− with high quenching efficiency Ksv and low detection limit, representing excellent selectivity and sensitivity. This work provides new perspectives for the development of lanthanide MOFs in detecting malachite green and heavy metal ions, possessing the potential applications in wastewater disposal and environmental protection.

Near-Infrared Emissive Lanthanide Metal-Organic Frameworks for Targeted Biological Imaging and pH-Controlled Chemotherapy.

Near-infrared window II (NIR-II, 1000-1700 nm) imaging displays the advantages in deep-tissue high-contrast imaging in vivo on the strength of the high temporal-spatial resolution and deeper penetration. However, the clinical utility of NIR-II imaging agents is limited by their single function. Herein, for the first time, we report the design of a multifunctional drug delivery system (DDS) assembly, CQ/Nd-MOF@HA nanohybrids, with NIR-II fluorescence (1067 nm), large Stokes shifts, and ultrahigh quantum yield, which combined targeted NIR-II luminescence bioimaging and pH-controlled drug delivery. The nanoscale metal-organic framework (MOF) as a highly promising multifunctional DDS for targeted NIR-II bioimaging and chemotherapy in vitro and in vivo lays the foundation of the MOF-based DDS for further clinical diagnosis and treatment.

MoS2 supported on Er-MOF as efficient electrocatalysts for hydrogen evolution reaction

The key to synthesis highly efficient MoS2 based electrocatalyst for hydrogen evolution reaction (HER) is to construct a reasonable composite system structure to improve the stability, reduce the aggregation and improve the intrinsic poor conductivity. In this paper, MoS₂ composite of erbium-based metal-organic framework (noted as Er-MOF/MoS2) were synthesized by hydrothermal method. The morphology and structure of the synthesized samples were characterized by powder X-ray diffraction (XRD), field emission electron microscopy (FESEM), scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS), and the electrocatalytic performances were tested by linear sweep voltammograms (LSV), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), i-t. On the basis of the experiment, Er-MOF/MoS2 shows improved conductivity and more exposed active sites, exhibiting excellent HER activity in acidic media, with only 234 mV overpotential to achieve 10 mA cm−2, and a Tafel slope of 54.3 mV dec−1. This strategy of porous structure of MoS2 composite rare earth metal organic framework materials provides a novel and effective solution for preparing high performance MoS2 based electrocatalyst.