Lanthanide Organic Frameworks Research Articles

High-Entropy Lanthanide-Organic Framework as an Efficient Heterogeneous Catalyst for Cycloaddition of CO2 with Epoxides and Knoevenagel Condensation.

Multimetallic synergistic effects have the potential to improve CO2 cycloesterification and Knoevenagel reaction processes, outperforming monometallic MOFs. The results demonstrate superior performance in these processes. To investigate this, we created and characterized a selection of single-component Ln(III)-MOFs (Ln = Eu, Tb, Gd, Dy, Ho) and high-entropy lanthanide-organic framework (HE-LnMOF) using solvent-thermal conditions. The experiments revealed that HE-LnMOF exhibited heightened catalytic efficiency in CO2 cycloesterification and Knoevenagel reactions compared to single-component Ln(III) MOFs. Moreover, the HE-LnMOF displayed significant stability, maintaining their structural integrity after five cycles while sustaining elevated conversion and selectivity rates. The feasible mechanisms of catalytic reactions were also discussed. HE-LnMOF possess multiple unsaturated metal centers, acting as Lewis acid sites, with oxygen atoms connecting the metal, and hydroxyl groups on the ligand serving as base sites. This study introduces a novel method for synthesizing HE-LnMOF and presents a fresh application of HE-LnMOF for converting CO2.

Synthesis of Stable 2D Conductive Lanthanide Organic Frameworks (Lu‐HHTP) for High‐Performance Humidity Sensors

Two‐dimensional conductive metal‐organic frameworks (MOFs) featuring structural diversity and high porosity represent promising platforms for chemiresistive humidity sensing. The precise control of the structure of lanthanide‐based MOFs and an exploration of its impact on charge transport and sensing applications have consistently been focal points for researchers. In this study, we present the synthesis and characterization of Lu‐HHTP (HHTP = 2,3,6,7,10,11‐hexahydroxytriphenylene) as highly crystalline and conductive porous materials. The polymeric framework of Lu‐HHTP encompasses 1D hexagonal channels and exhibits interlayer π‐π stacking, resulting in a material with a high surface area and uniform rod‐like microstructure. Benefiting from its elevated electrical conductivity, the Lu‐HHTP‐based humidity sensor exhibited commendable sensing properties within the relative humidity range of 33% to 95% at room temperature (25°C), achieving a response value as high as 19 at 95% relative humidity. Furthermore, the sensor displayed superior repeatability, characterized by rapid response and recovery speeds in the presence of moisture. These findings indicate that Lu‐HHTP holds substantial promise as a material for humidity sensors.

Enhanced CO2 Electrolysis Through Mn Substitution Coupled with Ni Exsolution in Lanthanum Calcium Titanate Electrodes.

In this study, perovskite oxides La0.3 Ca0.6 Ni0.05 Mnx Ti0.95- x O3- γ (x = 0, 0.05, 0.10) are investigated as potential solid oxide electrolysis cell cathode materials. The catalytic activity of these cathodes toward CO2 reduction reaction is significantly enhanced through the exsolution of highly active Ni nanoparticles, driven by applying a current of 1.2 A in 97% CO2 - 3% H2 O. The performance of La0.3 Ca0.6 Ni0.05 Ti0.95 O3-γ is notably improved by co-doping with Mn. Mn dopants enhance the reducibility of Ni, a crucial factor in promoting the in situ exsolution of metallic nanocatalysts in perovskite (ABO3 ) structures. This improvement is attributed to Mn dopants enabling more flexible coordination, resulting in higher oxygen vacancy concentration, and facilitating oxygen ion migration. Consequently, a higher density of Ni nanoparticles is formed. These oxygen vacancies also improve the adsorption, desorption, and dissociation of CO2 molecules. The dual doping strategy provides enhanced performance without degradation observed after 133h of high-temperature operation, suggesting a reliable cathode material for CO2 electrolysis.

Structure elucidation and topological studies of new lanthanide-organic frameworks (UPMOFs) synthesised via solvothermal route using mixed dicarboxylate linkers of 1,4-benzenedicarboxylic acid and 4,4-oxybis benzoic acid

The new lanthanide-organic frameworks (UPMOFs) were solvothermally synthesised using M(NO3)3·6H2O (M = La, Ce, Pr and Nd) metal salts with mixed dicarboxylate ligands namely, 1,4-benzenedicarboxylic acid (H2BDC) and 4,4-oxybis benzoic acid (H2OBA). The successful synthesis produced a series of four three-dimensional (3D) UPMOFs identified as [La(BDC)(OBA)(H2O)2].H2O (UPMOF710 (1)), [Ce(BDC)(OBA)(H2O)2].H2O (UPMOF711 (2)), [Pr(BDC)(OBA)(H2O)2].H2O (UPMOF712 (3)) and [Nd(BDC)(OBA)(H2O)2].H2O (UPMOF713 (4)). Comprehensive characterisations were performed on the newly synthesised UPMOFs, encompassing techniques such as infrared spectra (IR), powder X-ray diffraction (PXRD), thermal gravimetric analysis (TGA), scanning electron microscopy (SEM), Brunauer-Emmet-Teller (BET) and the structural elucidation was conducted using single-crystal X-ray diffraction (SCXRD). Notably, all four 3D UPMOFs were crystallised in a monoclinic sytem with different space groups. The UPMOFs (1) had a P21/n space group while the 2–4 were crystallised in the space group of I2/a. Consequently, the 2–4 UPMOFs are classified as isostructural MOFs. Remarkably, the topological analysis unveiled a novel topology denoted as upm, which has not been observed in the realm of reticular chemistry.

Syntheses, crystal structures and properties of a series of isostructural lanthanide organic frameworks

We have successfully constructed nine isostructural Ln-MOFs with the formula Ln(L)1.5(H2O)2·H2O (1-Ce, 2-Dy, 3-Eu, 4-Gd, 5-Ho, 6-Nd, 7-Pr, 8-Sm, and 9-Tb) wherein the dihydroxy groups did not participate in coordination.

Mixed lanthanide-organic frameworks with borono group for colorimetric detection of excess fluoride levels in river

Chronic fluoride (F−) toxicity has been endemic at least 25 countries around the world due to prolonged consumption of contaminated water, posing great threat to human health. Rapid and convenient...

In-situ self-assembly of two ultrastable bifunctional Keggin-type polyoxometalates-based zeolite-like frameworks for efficient cascade biomass chemicals conversion

The cascade conversion of 5-hydroxymethylfurfural (HMF) using a single-component catalyst to produce valuable biomass chemicals represents a challenging and intriguing area for investigation. In this study, we present the remarkable potential of two ultrastable polyoxometalates-based zeolite-like frameworks (PZFs), {[La(H2O)3Cl0.5(pdc)][La(H2O)4(pdc)]}2[PMo12O40]·2H2O (PZF-1) and [La(H2O)4(pdc)]4[SiW12O40]·2H2O (PZF-2) (H2pdc = pyridine-2,6-dicarboxylate) that can be self-assembled from the commercialized raw materials by the facile hydrothermal reaction under the controllable pH environments and their cascade conversion of biomass chemicals for the first time. The structural analyses have unequivocally demonstrated the in-situ formation of Keggin-type polyoxometalates, which are encapsulated within the cationic Lewis-acid Lanthanide-organic frameworks. The syntheses yield highly stable and tolerant crystalline bifunctional PZFs catalysts, capable of withstanding thermal conditions (up to 425 °C) and a wide pH range (pH = 1–11) far better than those reported cases. Most notably, PZF-1 demonstrated outstanding catalytic performance in the cascade reactions of HMF oxidation and 2,5-diformylfuran (DFF) Knoevenagel condensation, achieving remarkable yields of up to 99 %. The structure of PZF-1 remained well-preserved even after undergoing five cycles of catalytic reaction. These encouraging findings provide a solid foundation for the further development of PZFs catalysts for the advancement of biomass conversion processes.

VIS/NIR double-domain luminescence sensing with anti-interference performance by a lanthanide-organic framework nanosheet loaded with atomically dispersed Cu sites

Fluorescence/luminescence detection has garnered extensive attention due to its remarkable sensitivity and selectivity within the visible (VIS) and near-infrared (NIR) spectrum. However, detection in the VIS domain is susceptible to interference from background fluorescence and internal quenching effects; the reliability and stability of NIR detection are constrained by its luminescence efficiency and lifetime. In this context, we introduce a dual-domain detection strategy under both VIS and NIR illumination, leveraging the advantages of both domains to achieve anti-interference luminescence detection of tetracycline hydrochloride (TC). Specifically, Cu2+ ions were incorporated into Yb-TCPP nanosheets (H2TCPP = 5,10,15,20-tetra-(4-carboxyphenyl) porphyrin) and anchored at the porphyrin core of the TCPP2- ligand, forming highly dispersed Cu-N4 sites. Notably, the Cu@MOF luminescent material exhibited a picomolar level dual-domain fluorescence/luminescence response towards TC: it activates detection in the VIS domain and turns off in the NIR domain. Largely due to this dual-domain response, the sensor showcases excellent anti-interference capabilities and reliability. When the VIS domain is perturbed, the sensor's detection in the NIR domain remains unaffected; conversely, interference in the NIR domain barely impacts the sensor's behavior in the VIS domain. Furthermore, a systematic mechanistic analysis suggests that the introduction of atomically dispersed Cu2+ sites not only enhances the acid-base interaction sites between the sensor and the analyte but also amplifies the adsorption capacity towards the analyte, effectively reducing detection limits and bolstering anti-interference capabilities. Anticipating the future, this detection strategy holds promise in offering a more cost-effective, reliable, and interference-resistant option for commercial detection, signaling a bright prospect for its development.

Colorimetric fluorescence determination of anthrax biomarker using a bimetallic lanthanide metal–organic framework

Bacillus anthracis is toxic bacterial spore that cause human anthrax infections. Therefore, rapid and sensitive detection of Bacillus anthracis or its main biomarker 2, 6-pyridine dicarboxylic acid (DPA) is of great significance. Herein, a series of lanthanide–organic frameworks (Tb/Eu-MOF-1–6) were synthesized by the solvothermal reactions of 2,2′-bipyridine-6,6′-dicarboxylic acid (H2BPDC) with Eu3+ and Tb3+. Among these samples, Tb/Eu-MOF-6 exhibited selective detection of DPA with self-calibrating and colorimetric fluorescence determination. The sensitivity of Tb/Eu-MOF-6 revealed a linear response of ln (IN) = -10.896CDPA + 0.14366 with a limit of detection with 4.51 μM. The emission color of Tb/Eu-MOF-6 observed with the naked eye, turned yellow to red after introducing appropriate concentration of DPA.The energy-transfer behavior between BPDC2- Tb3+, and Eu3+ was systematically studied, which primarily controlled the sensitivity of detection. With the combined merits of self-calibrating, rapid and naked-eye recognition of DPA, Tb/Eu-MOF-6 can be counted as a promising contender for anthrax biomarker detection.

Straw-bundle-like rare earth metal-organic frameworks derivatives for high-efficiency electromagnetic wave absorption

Metal-organic frameworks (MOFs) derivatives have been widely developed as electromagnetic wave (EMW) absorption materials. Nevertheless, owing to the diverse metal ions, organic ligands, and crystal morphologies of MOFs precursors, challenges still remain to overcome towards directly ascertaining the contribution of metal components on EMW absorption for precisely designing high EMW absorption performance of MOF derivatives. Here, we synthesize a series of rare earth (RE) MOF derivatives via a facile, scalable coprecipitation followed by carbonization approach. Thanks to the similar chemical property derived from lanthanide shrinkage of RE elements, the MOF-derived RE oxides (REO)/carbon (REO = CeO2, La2O3, Nd2O3) hybrids exhibit the identical straw-bundle-like microstructure, efficiently assisting the elucidation of the roles of metal components in promoting EMW absorption. Benefiting from the tunable bandgap of various REO as well as carbonization temperature, the 800 °C-carbonized CeO2/carbon shows a minimum reflection loss of − 58.7 dB at a thickness of 1.7 mm and an effective absorption bandwidth of 5.0 GHz, comparable to the best EMW absorbers. This work not only demonstrates novel, high-performance RE-MOF derivatives, but also offers a general yet efficient strategy for designing metal components to achieve high-efficiency MOF-based EMW absorbers.

Lanthanide 3D Supramolecular Framework Boosts Stable Perovskite Solar Cells with High UV Utilization.

In this work, the ligand-to-metal charge transition and Förster resonance energy transfer process is exploited to derive lanthanide-organic framework (Tb-cpon) modified perovskite solar cells (PSCs) with enhanced performance under UV irradiation. Tb-cpon-modified PSCs exhibit rapid response and reduced degradation due to energy downconversion facilitated by effective coupling of UV-sensitive chromophores to lanthanide luminescent centers, enhancing the spectral response range of the composite films. Furthermore, the characteristic changes of precursor particle sizes suggest formation of Tb-cpon adducts as intermediate products, leading to enhanced crystallinity and reduced defect concentrations in the Tb-cpon-perovskite hybrid film. Accordingly, the Tb-cpon-modified PSC devices obtain a champion efficiency up to 23.72% as well as a sensitive photovoltaic conversion even under pure UV irradiation. Moreover, the unencapsulated devices maintain more than 80% of the initial efficiency after continuous irradiation under a 310nm UV lamp for 24h (from the Au electrode side), compared to 21% for the control devices.

Robust Fluorine-Functionalized {Ln5}-Organic Frameworks for Excellent Catalytic Performance on Cycloaddition of CO2 with Epoxides and Knoevenagel Condensation.

Lanthanide-organic frameworks (LnOFs) are a class of promising catalysts on a large number of organic reactions because of the higher coordination number of Ln3+ ions, inspired by which exploratory preparation of cluster-based LnOFs was carried out by us. Herein, the exquisite combination of spindly [Ln5(μ3-OH)6(CO2)6(H2O)6] clusters (abbreviated as {Ln5}) and fluorine-functionalized tetratopic ligand of 2',3'-difluoro-[p-terphenyl]-3,3″,5,5″-tetracarboxylic acid (F-H4PTTA) engendered two highly robust isomorphic nanoporous frameworks of {[Ln5(FPTTA)2(μ3-OH)6(H2O)6](NO3)}n (NUC-61, Ln = Ho and Dy). NUC-61 compounds are rarely reported {Ln5}-based 3D frameworks with nano-caged voids (19 Å × 17 Å), which are shaped by twelve [Ln5(μ3-OH)6(COO)8] clusters and eight completely deprotonated F-PTTA4- ligands. Activated NUC-61a compounds are characterized by plentiful coexisted Lewis acid-base sites of open LnIII sites, capped μ3-OH, and -F. Judged by the ideal adsorbed solution theory (IAST), activated NUC-61Ho-a had a high CO2/CH4 adsorptive selectivity with the value of 12.7 (CO2/CH4 = 50/50) and 9.1 (CO2/CH4 = 5/95) at 298 K, which could lead to high-purity CH4 (≥99.9996%). Furthermore, catalytic experiments exhibited that NUC-61Ho-a, as a representative, could efficiently catalyze the cycloaddition reactions of CO2 with epoxides as well as the Knoevenagel condensation reactions of aldehydes and malononitrile. This work proves that the {Ln5}-based skeletons of NUC-61 with chemical stability, heterogeneity, and recyclability are an excellent acid-base bifunctional catalyst for some organic reactions.

Near-Unity Energy Transfer from Uranyl to Europium in a Heterobimetallic Organic Framework with Record-Breaking Quantum Yield.

Lanthanide organic frameworks (Ln-MOFs) have attracted increasing research enthusiasm as photoluminescent materials. However, limited luminescence efficiency stemming from restricted energy transfer efficiency from the organic linker to the metal center hinders their applications. Herein, a uranyl sensitization approach was proposed to boost the luminescence efficiency of Ln-MOFs in a distinct heterobimetallic uranyl-europium organic framework. The record-breaking photoluminescence quantum yield (PLQY, 92.68%) among all reported Eu-MOFs was determined to benefit from nearly 100% energy transfer efficiency between UO22+ and Eu3+. Time-dependent density functional theory and ab initio wave-function theory calculations confirmed the overlap of excited state levels between UO22+ and Eu3+, which is responsible for the efficient energy transfer process. Coupled with intrinsically strong stopping power toward X-ray of the uranium center, SCU-UEu-2 features an ultralow detection limit of 1.243 μGyair/s, outperforming the commercial scintillator LYSO (13.257 μGyair/s) and satisfying the requirement of X-ray diagnosis (below 5.5 μGyair/s) in full.

Highly thermostable mixed lanthanide organic frameworks with high quantum yield for warm white light-emitting diodes.

A mixed lanthanide organic framework was prepared via hydrothermal methods using m-phthalic acid (m-H2BDC), 1,10-phenanthroline (1,10-Phen), and Ln3+ ions, formulated as [HNMe2][Eu0.095Tb1.905(m-BDC)3(phen)2] (ZTU-6). The structure and stability of ZTU-6 were characterised by X-ray diffraction (XRD) and thermogravimetric analysis (TGA), which revealed a three-dimensional pcu topology with high thermal stability. Fluorescence tests showed that ZTU-6 emitted orange light with a high quantum yield of 79.15%, and it can be effectively encapsulated in a light-emitting diode (LED) device emitting orange light. In addition, ZTU-6 was found to be compatible with BaMgAl10O17:Eu2+ (BAM) blue powder and [(Sr,Ba)2SiO4:Eu2+] silicate yellow and green powder to create a warm white LED with a high colour rendering index (CRI) of 93.4, a correlated colour temperature (CCT) of 3908K, and CIE coordinates of (0.38, 036).

Stable Lanthanide–Organic Frameworks: Crystal Structure, Photoluminescence, and Chemical Sensing of Vanillylmandelic Acid as a Biomarker of Pheochromocytoma

Several isostructural lanthanide metal-organic frameworks, viz. [Ln(DCHB)1.5phen]n (Ln-MOFs, where Ln = Eu for 1, Tb for 2, Sm for 3 and Dy for 4), are successfully synthesized through the hydrothermal reactions of 4'-di(4-carboxylphenoxy)hydroxyl-2, 2'-bipyridyl (H2DCHB) and lanthanide nitrates as well as chelator 1,10-phenantroline (phen). These structures are characterized by single-crystal X-ray diffraction, and the representative Ln-MOF 1 is a fivefold interpenetrated framework with the uncoordinated Lewis base N sites form DCHB2- ligands. The photoluminescence research studies reveal that Ln-MOFs 1-4 exhibit characteristic fluorescent emissions from ligand-induced lanthanide Ln(III) ions, while the single-component emission spectra of Ln-MOF 4 are all located in a white region under different excitations. The absence of coordinated water and the interpenetration property of the structures are conducive to the structure rigidity, and the results display that Ln-MOF 1 has high thermal/chemical stabilities in common solvents and a wide pH range as well as the boiling water. Notably, luminescent sensing studies reveal that Ln-MOF 1 with prominent fluorescence properties can perform in highly sensitive and selective sensing of vanillylmandelic acid (VMA) in aqueous systems (KSV = 562.8 L·mol-1; LOD = 4.6 × 10-4 M), which can potentially establish a detection platform for the diagnosis of pheochromocytoma via multiquenching mechanisms. Moreover, the 1@MMMs sensing membranes comprised of Ln-MOF 1 and a poly(vinylidene fluoride) (PVDF) polymer can also be facilely developed for VMA detection in aqueous media, suggesting the enhanced convenience and efficiency of practical sensing applications.

Three-Dimensional Viologen-Based Lanthanide-Organic Frameworks: Photochromism and Fluorescence Detection of Quinolone Antibiotics.

Quinolone antibiotic residues, norfloxacin (NORF) and ciprofloxacin (CIP), have attracted more attention due to their frequent detection in surface water and food field, which seriously threaten the health of animals and humans. Rapid and efficient detection of NORF and CIP is critical for environmental testing and ecosystems. Herein, two novel isostructural viologen-functionalized Ln(III) complexes [Ln2L0.5(IPA)3]n (Ln = Eu, 1; Tb, 2; L = N,N'-bis (2-carboxyethyl)-4,4'-bipyridridylium dichloride, H2IPA = isophthalic acid) with a three-dimensional structure have been synthesized solvothermally. Complexes 1 and 2 exhibited reversible photochromism under UV light. In addition, complex 1 exhibits excellent pH tolerance and can be seen as an efficient fluorescent probe for the detection of NORF and CIP with detection limits of 7.90 × 10-7 and 9.48 × 10-7 M, respectively. Furthermore, the good photoresponsive and outstanding fluorescent properties of 1 were further exploited in dual-function paper involving erasable inkless printing and detection of NORF and CIP. Our work reports a new strategy for recognizing NORF and CIP based on the luminescent color change of the viologen-based Ln-MOFs, providing a new direction for the development of multifunctional materials.

Construction of Water-Stable Rare-Earth Organic Frameworks with Ambient High Proton Conductivity Based on Zirconium Sandwiched Heteropolytungstate.

Water-stable proton-conducting materials owning excellent performances at ambient temperatures are currently one of the crucial challenges. Herein, four water-stable three-dimensional polyoxometalate-based rare-earth organic frameworks have been successfully synthesized and formulated as H{Ln4(L)2(H2O)21[Zr3(OH)3(PW9O34)2]}·15H2O (1-3) (Ln = La (1), Ce (2), Pr (3); L = 3,5-pyridine dicarboxylic acid), which are the first examples of MOFs constructed by a zirconium sandwiched polyoxoanion. There are abundant coordinated water molecules functionalizing the PrIII centers, and simultaneously, plenty of lattice water molecules are fitted into the channel of the framework. A continuous H-bonding network is found between the architectures and plays an important role in stabilizing the structure. Benefiting from the consecutive H-bonding networks, compounds 1-3 showed high proton conductivities at ambient temperature (up to 1.05 × 10-3 S·cm-1 under 98% RH) by a synergistic effect of the combined components.

Recyclable luminescence sensor for Cu2+, Cr2O72− and CrO42− in water and acid/base vapor response based on water-stable bipyridyl-based Ln-MOFs

Detecting toxic contaminants in water, such as heavy metal ions and chromate ions, is important for public health and the environment. In the context, luminescence lanthanide-organic frameworks have been the competitive means to recognize such contaminants. Herein, two Ln-MOFs, [Ln3(L)2(HCOO)(H2O)5]·14H2O (H4L ​= ​2,6-di(2,4-dicarboxyphenyl)-4-(pyridine-4-yl)pyridine) (Ln ​= ​Eu, 1-Eu and Ln ​= ​Tb, 1-Tb), have been synthesized solvothermally by using the selection of the bipyridyl-tetracarboxylic ligand (H4L). Single-crystal X-ray diffraction indicates that this two Ln-MOFs are isostructural and contain uncoordinated pyridyl nitrogen atoms and water molecules, which provides the Lewis-base sites for detecting various small molecules. Moreover, both 1-Eu and 1-Tb exhibit excellent chemical stability in aqueous solution with the pH ranging from 2 to 13. Thanks to such characteristics, 1-Eu can be served as a multi-responsive luminescence sensor for Cu2+, Cr2O72− and CrO42− in deionized water, tap water and river water via luminescent quenching. Notably, the sensing processes toward Cu2+, Cr2O72− and CrO42− exhibit high selectivity and sensitivity, and good recyclability. The luminescence sensing mechanism was carefully studied by PXRD, XPS, and UV spectroscopy. In addition, 1-Eu also displays luminescence turn-off/on when alternately exposed to HCl and NH3 gases, which can mainly be attributed to the protonation/deprotonation process by the free bipyridyl N sites. The work illustrates 1-Eu could shed light on the exploration of MOF-based sensors for analytical applications.

Recyclable Luminescent Sensor for Detecting Creatinine Based on a Lanthanide-Organic Framework.

Creatinine is an important clinical marker for human health, but detecting it by a luminescent sensor based on metal-organic frameworks is rarely investigated. In this work, we synthesized a new lanthanide-organic framework {[Tb(L)(CH3COO)(H2O)]·0.5DMF}n (1) (H2L = 3,5-bis(4'-carboxy-phenyl)1,2,4-triazole) with good solvent and acid/alkaline stabilities. Experimental results indicate that 1 can be used in the detection of creatinine in an aqueous solution with a wide linear detection range from 3.27 to 371 μM, and the detection limit can reach 1.7 × 10-6 M based on the 3σ method, which is less than the pathogenic concentration in a real environment. In addition, this luminescent sensor can also monitor the concentration changes of creatinine in diluted serum solutions and can be recycled at least five times, suggesting that it has a potential application for clinical monitoring.

Efficient Xe/Kr Separation Based on a Lanthanide-Organic Framework with One-Dimensional Local Positively Charged Rhomboid Channels.

Efficient xenon/krypton (Xe/Kr) separation has played an important role in industry due to the wide application of high-purity Xe and with regard to the safe disposal of radioactive noble gases (85Kr and 133Xe). A less energy-demanding separation technology, adsorptive separation using porous solid materials, has been proposed to replace the traditional cryogenic distillation with intensive energy consumption. As a cutting-edge class of porous materials, metal-organic frameworks (MOFs) featuring permanent porosity, designable chemical functionalities, and tunable pore sizes hold great promise for Xe/Kr separation. Here, we report a two-dimensional (2D) lanthanide-organic framework (termed LPC-MOF, [Eu(Ccbp)(NO3)(HCOO)]·DMF0.3(H2O)2.5) with one-dimensional (1D) local positively charged rhomboid channels whose size matches well with the kinetic diameter of Xe, leading to its superior Xe/Kr separation performance. Column breakthrough experiments demonstrate that LPC-MOF exhibits a high Xe/Kr selectivity of 12.4 and an Xe adsorption amount of 3.39 mmol kg-1 under simulated conditions for real used nuclear fuel (UNF)-reprocessing plants. Furthermore, density functional theory (DFT) calculations elucidate not only the intrinsic mechanisms of Xe/Kr separation at the molecular level but also the detailed influence of the local positive charge (N+) on the performance of Xe/Kr separation in the MOF system.