Hybrid Metal Organic Frameworks Research Articles

Fully fluorinated hybrid zeolite imidazole/Prussian blue analogs with combined advantages for efficient oxygen evolution reaction

Hybrid metal-organic framework (MOF) derivatives play a significant role in the novel catalyst development in energy conversion reactions. Here, we demonstrated the low-temperature fully fluorinated zeolitic imidazole framework (ZIF) coupled with a three-dimensional open framework Prussian blue analog (PBA) with combined advantages for electrocatalytic oxygen evolution reaction (OER) in water splitting reaction. The spectroscopic analysis and the electrochemical studies revealed the combined advantages of efficient electronic effect and active site synergism. Because of good conductivity improvement by N-doped carbon derived from ZIF and the high electrochemical surface area and active site exposure from PBA derivatives, good catalytic performance was obtained on the optimal catalyst of CoNi ZIF/CoFe-PBA-F-300, which required a low overpotential of 250 mV to reach 10 mA/cm2 loaded on the glassy carbon electrode, with Tafel slope of 47.4 mV/dec, and very high dynamic and steady stability. In addition, the multi-component with the mixed structure from highly polar metal fluorides promoted the easy formation of the active phase as revealed by the post-sample analysis. The current results showed a novel composite catalyst materials development from the hybrid MOF derivatives, which would be promising in the electrolysis of water oxidation reactions and energy-relevant catalysis reactions.

Recent Advances in Ionic Liquids—MOF Hybrid Electrolytes for Solid-State Electrolyte of Lithium Battery

Li-ion batteries are currently considered promising energy storage devices for the future. However, the use of liquid electrolytes poses certain challenges, including lithium dendrite penetration and flammable liquid leakage. Encouragingly, solid electrolytes endowed with high stability and safety appear to be a potential solution to these problems. Among them, ionic liquids (ILs) packed in metal organic frameworks (MOFs), known as ILs@MOFs, have emerged as a hybrid solid-state material that possesses high conductivity, low flammability, and strong mechanical stability. ILs@MOFs plays a crucial role in forming a continuous interfacial conduction network, as well as providing internal ion conduction pathways through the ionic liquid. Hence, ILs@MOFs can not only act as a suitable ionic conduct main body, but also be used as an active filler in composite polymer electrolytes (CPEs) to meet the demand for higher conductivity and lower cost. This review focuses on the characteristic properties and the ion transport mechanism behind ILs@MOFs, highlighting the main problems of its applications. Moreover, this review presents an introduction of the advantages and applications of Ils@MOFs as fillers and the improvement directions are also discussed. In the conclusion, the challenges and suggestions for the future improvement of ILs@MOFs hybrid electrolytes are also prospected. Overall, this review demonstrates the application potential of ILs@MOFs as a hybrid electrolyte material in energy storage systems.

Adsorption of Phenol from Both Acidic and Basic Industrial Waste via Newly Synthesized Metal Organic Framework Hybrid Smart Adsorbents

Newly prepared pH-responsive metal organic frameworks (MOFs) having a specific surface area of 1400 m2/g could be exploited in the total removal of pollutants from wastewaters in this work. Smart core–shell structures of COP-150@ZIF-8 and NPC@ZIF-8 were successfully synthesized in large scales through internal extended growth under polyvinylpyrrolidone (PVP) regulation and used in phenol removal from aqueous media. The essential factors on the removal, namely pH, initial concentration of phenol, contact time, adsorbent dosage, and temperature, were studied and optimized. The experimental data were investigated by different kinetic and isotherm models, in which the removal of phenol by these smart sorbents is correlated with the Freundlich isotherm model and was found to follow the pseudo-second-order kinetic model. Excellent adsorption capacity of 1670 mg·g–1 and high efficiency were achieved in phenol removal (mixing time of only 20 min) that suggest the application of smart NPC@ZIF-8 core–shell in water filtration. Also, the optimal concentration of smart NPC@ZIF-8 and smart COP@ZIF-8 core–shell adsorbents was obtained as 300 and 250 mg·L–1, respectively. On the other hand, more than 94% removal of phenol was observed at pH = 3 for both smart nanosorbents (mere use of 0.1 g adsorbent). The results of thermodynamics confirm that the process of adsorption is exothermic and spontaneous. Moreover, having simulated the atomistic investigation of phenol removal via molecular dynamics, it was concluded that the different designed adsorbents in this work have a high capacity to remove phenol, specifically NPC@ZIF-8.

Fabricating Materials of Institute Lavoisier-53(Fe)/zeolite imidazolate framework-8 hybrid materials as high-efficiency and reproducible adsorbents for removing organic pollutants

Environmental pollution by emerging contaminants has become an urgent problem. Herein, novel binary metal–organic framework hybrids were constructed from Materials of Institute Lavoisier-53(Fe) (MIL-53(Fe)) and zeolite imidazolate framework-8 (ZIF-8) for the first time. A battery of characterizations were employed to determine the MIL/ZIF hybrids' properties and morphology. Furthermore, the MIL/ZIF towards toxic antibiotics (tetracycline, ciprofloxacin and ofloxacin) were studied to explore their adsorption abilities. The present work disclosed that the obtained MIL-53(Fe)/ZIF-8 = 2:3 possessed an eminent specific surface area with an admirable removal efficiency of tetracycline (97.4%), ciprofloxacin (97.1%) and ofloxacin (92.4%), respectively. The tetracycline adsorption process conformed to the pseudo-second-order kinetic model and this process was more compatible with the Langmuir isotherm model with the highest adsorption capacity of 215.0 mg g−1. Moreover, the process of removing tetracycline was proved to be spontaneous and exothermic by the thermodynamic results. Furthermore, the MIL-53(Fe)/ZIF-8 = 2:3 towards tetracycline exhibited significant regeneration ability. The effects of pH, dosage, interfering ions and oscillation frequency on tetracycline adsorption capacity and removal efficiency were also investigated. The primary factors contributing to the decent adsorption ability between MIL-53(Fe)/ZIF-8 = 2:3 and tetracycline included electrostatic, π–π stacking, hydrogen bonding and weak coordination interactions. Additionally, we also investigated the adsorption ability in real wastewater. Thus, the proposed binary metal–organic framework hybrid materials can be deemed a promising adsorbent in wastewater purification.

Bimetallic FeCo metal-organic-frameworks anchored multi-walled carbon nanotubes for electrochemical nitrite sensing

A heterostructured nanocomposite modified electrode was designed as a sensitive and efficient analytical tool for nitrite determination. The nanocomposite constructed from different building blocks was fabricated by ultrasonically growing bimetallic FeCo metal-organic framework (MOF) in the well-dispersed multi-walled carbon nanotubes (MWCNTs) suspensions at room temperature, where the MOF hybrid was extended to uniform thin film structure. Electrochemical experimental results demonstrate that the synergistic contributions from bimetallic active sites, MWCNTs and thin-film morphology endow modified electrode with dramatically enhanced catalytic activity metrics towards nitrite. Significantly, the co-doping of Fe-Co plays key role in improving the electronic conductivity and catalytic capacity of the MOF/MWCNTs composite. Thereinto, the FeCo-MOF/MWCNTs sensor displays excellent detection performance with a wide linear detection range (5∼5000 μM), outstanding selectivity and a detect limitation of 1.68 μM for nitrite. These superior findings provide new potentials application for the inspection of nitrite in environmental monitor.

Enhanced performance of ZIF-8 nanocrystals hybrid monolithic composites via an in-situ growth strategy for efficient capillary microextraction of perfluoroalkyl phosphonic acids

Enrichment of perfluoroalkyl phosphonic acids (PFPAs) is of great significance and challenging for environmental monitoring, due to their toxic and persistent nature, highly fluorinated character as well as low concentration. Herein, novel metal-organic frameworks (MOFs) hybrid monolithic composites were prepared via metal oxide-mediated in situ growth strategy and utilized for capillary microextraction (CME) of PFPAs. A porous pristine monolith was initially obtained by copolymerization of the zinc oxide nanoparticles (ZnO-NPs)-dispersed methacrylic acid (MAA) with ethylenedimethacrylate (EDMA) and dodecafluoroheptyl acrylate (DFA). Afterwards, nanoscale-facilitated transformation of ZnO nanocrystals into the zeolitic imidazolate framework-8 (ZIF-8) nanocrystals was successfully realized via the dissolution-precipitation of the embedded ZnO-NPs in the precursor monolith in the presence of 2-methylimidazole. Experimental and spectroscopic results (SEM, N2 adsorption-desorption, FT-IR, XPS) revealed that the coating of ZIF-8 nanocrystals significantly increased the surface area of the obtained ZIF-8 hybrid monolith and endowed the material abundant surface-localized unsaturated zinc sites. The proposed adsorbent showed highly enhanced extraction performance for PFPAs in CME, which was mainly ascribed to the strong fluorine affinity, Lewis acid/base complexing, anion-exchange, and weakly π-CF interaction. The coupling of CME with LC-MS enables effective and sensitive analysis of ultra-trace PFPAs in environment water and human serum. The coupling method demonstrated low detection limits (2.16–4.12 ng L−1) with satisfactory recoveries (82.0–108.0%) and precision (RSDs ≤6.2%). This work offered a versatile route to design and fabricate selective materials for emerging contaminant enrichment in complicated matrices.

Ionic liquid hybrid metal–organic frameworks for efficient adsorption and selective separation of ammonia at high temperature

Efficient adsorption and selective separation of ammonia at high temperature is a crucial and challenging issue. In this work, a series of stable ionic liquid hybrid materials have been developed by simple impregnation of ionic liquids into stable metal–organic framework Al-fum with 1D pores. The hybrid material [C2N][Zn3Cl7]@Al-fum-60% exhibited an exceptionally high uptake (9.9 mmol/g at 80 °C, 8.8 mmol/g at 100 °C) at high temperature, excellent uptake (9.8 mmol/g at 25.0 °C) at low ammonia concentration (100,000 ppm), and remarkable selective separation performance (selectivity factor is 25.1) of NH3 from NH3/CO2 mixture at high temperature. The NH3 uptake of [C2N][Zn3Cl7]@Al-fum-60% at 100 °C was higher than the capacity of most of typical porous NH3 adsorbents at room temperature. It is revealed that such superior NH3 capacity and selective separation performance are mainly attributed to coordination interactions of NH3 to Zn centre of the ionic liquids and the hydrogen bonding interactions of NH3 with Cl of the ionic liquids and NH3 with μ-OH of Al-fum.

Controllable growth of drug-encapsulated metal-organic framework (MOF) on porphyrinic MOF for PDT/chemo-combined therapy

To improve the therapeutic effect of tumors, developing well-defined hybrid metal-organic frameworks (MOFs) through MOF-on-MOF growth has attracted much attention. In this work, an in situ growth strategy was reported to assemble doxorubicin (DOX)-encapsulated zeolitic imidazolate frameworks (ZIF-8) on the surface of Zr(IV)-based porphyrinic MOFs. Such an approach offers a high controllability in the thickness of the ZIF-8 layer without any requirement of surface modifications on porphyrinic MOFs. Impressively, the acidic pH-response degradation of ZIF-8 promoted the release of DOX in the acidic tumor microenvironment. Upon light irradiation, porphyrinic MOFs can harvest photons to produce plentiful singlet oxygen, thus leading to amplified chemo/PDT therapeutic efficacy. This work paves the way to utilize the hybrid engineering of MOFs for synergistic cancer therapy.

Hg2+ removal from wastewater by anchoring nitrogen/sulfur active center onto metal-organic framework via Schiff-base reaction: Synthesis, characterization, and experiment

Remediation of Hg2+ pollution in wastewater is imminent. Herein, a Metal-Organic Framework hybrid Uio-DBD-x was designed and synthesized via rational introducing the 5-Diamino-1,4-benzenedithiol Dihydrochloride (DBD) molecule onto parent Uio-66-NH2. By optimizing the synthesis conditions, the material exhibited better adsorption performance when x = 1. The characteristics including crystallinity, morphology, and pore size were analyzed. 12.64 nm for pore diameter and 493.73 m2/g for surface areas of Uio-DBD-1 were obtained. Subsequently, the adsorption performance of Uio-DBD-1 towards Hg2+ was studied under different pH, dosage, concentration, and time. The corresponding maximum adsorption capacity of 423.10 mg/g and equilibrium time of 10 min was achieved. Remarkably, Hg2+ concentration could be reduced below the emission limit (0.05 mg/L). Furthermore, the selectivity and reusability of the adsorbent were investigated, and the results manifested that Uio-DBD-1 maintains high removal efficiency (82.10%) after 6 times recycles. The possible adsorption mechanism could be ascribed to the strong interaction (chelation, proton exchange, and coordination) between Hg2+ and –NH2/-SH groups. This work breaks new ground in functional material design and paves the way for wastewater treatment.

A carbon catalyst doped with Co and N derived from the metal-organic framework hybrid (ZIF-8@ZIF-67) for efficient oxygen reduction reaction

A carbon catalyst doped with Co and N derived from the metal-organic framework hybrid (ZIF-8@ZIF-67) for efficient oxygen reduction reaction

Efficient capture of fluoroquinolones in urine and milk samples with multi-monolith fibers solid phase microextraction based on hybrid metal–organic framework/monolith material

To capture fluoroquinolones (FQs) from complex samples efficiently, a new hybrid metal–organic framework (MOF)@monolith material (HMM) was fabricated and employed as the extraction medium of multi-monolith fibers solid phase microextraction (MMF-SPME). Porous monolithic fibers based on allyltrimethylammonium chloride-co-ethylene glycol dimethacrylate/divinylbenzene polymer were fabricated firstly. After that, the strategy of layer-by-layer self-assembly was employed to prepare zeolitic imidazolate frameworks within the pores and the surface of the monolith. Various characterization results well evidenced that the introduction of MOF not only enhanced the surface area of adsorbent, but also introduced new active sites. The prepared HMM/MMF-SPME presented satisfactory capture performance towards studied FQs by multiple interactions. Enrichment factors of FQs in human urine and milk samples were in the ranges of 99–128 and 85–121, respectively. Under the most beneficial fabrication and extraction parameters, HMM/MMF-SPME was combined with high-performance liquid chromatography to quantify trace FQs in urine and milk samples. High sensitivity (limits of detection were 0.0072–0.031 μg/L for urine sample and 0.016–0.057 μg/kg for milk sample) and good precision (RSDs below 10%) were obtained. In the analysis of FQs in actual samples, the recovery at different spiked contents varied from 77.4% to 120%, with good reproducibility. Accuracy and reliability of established approach were well verified with confirmation experiments. Satisfactory results evidence that the developed HMM/MMF-SPME can be a prominent technique for the capture of trace FQs in complex samples.

MOF-Derived CoNi Nanoalloy Particles Encapsulated in Nitrogen-Doped Carbon as Superdurable Bifunctional Oxygen Electrocatalyst

Carbon-encapsulated transition metal catalysts have caught the interest of researchers in the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) due to their distinctive architectures and highly tunable electronic structures. In this work, we synthesized N-doped carbon encapsulated with CoNi nanoalloy particles (CoNi@NC) as the electrocatalysts. The metal-organic skeleton ZIF-67 nanocubes were first synthesized, and then Ni2+ ions were inserted to generate CoNi-ZIF precursors by a simple ion-exchange route, which was followed by pyrolysis and with urea for the introduction of nitrogen (N) at a low temperature to synthesize CoNi@NC composites. The results reveal that ZIF-67 pyrolysis can dope more N atoms in the carbon skeleton and that the pyrolysis temperature influences the ORR and OER performances. The sample prepared by CoNi@NC pyrolysis at 650 °C has a high N content (9.70%) and a large specific surface area (167 m2 g-1), with a positive ORR onset potential (Eonset) of 0.89 V vs. RHE and half-wave potential (E1/2) of 0.81 V vs. RHE in 0.1 M KOH, and the overpotential of the OER measured in 1 M KOH was only 286 mV at 10 mA cm-2. The highly efficient bifunctional ORR/OER electrocatalysts synthesized by this method can offer some insights into the design and synthesis of complex metal-organic frameworks (MOFs) hybrid structures and their derivatives as functional materials in energy storage.

Nanoarchitecting a Dual Z-Scheme Zr-MOF/Ti-MOF/g-C3N4 Heterojunction for Boosting Gomberg–Buchmann–Hey Reactions under Visible Light Conditions

Combining more than two metal–organic frameworks (MOFs) with different structures is an intelligent strategy for the architecture of hybrid MOFs. Herein, well-organized UiO-66(Zr)-on-MIL-125(Ti)-NH2 growth with g-C3N4 nanosheets was developed for the Gomberg–Buchmann–Hey reaction under visible light irradiation (λ > 420 nm). First, UiO-66(Zr) micropores as host MOFs were fabricated by a solvothermal method. Subsequently, MIL-125(Ti)-NH2 crystals and g-C3N4 nanosheets were grown inside UiO-66(Zr) to obtain a new type of the dual Z-scheme Zr-MOF/Ti-MOF/g-C3N4 heterojunction photocatalyst. Under visible light irradiation, this dual Z-scheme heterojunction acts as a highly efficient photocatalyst for forming C–C bonds via diazonium salts, which can compete with the best photocatalyst systems. The findings indicated that the presence of Zr and Ti metals in MOF-on-MOF and g-C3N4 nanosheets could significantly increase the separation of photogenerated electron–hole pairs and then enhance the photocatalytic performance. The present study not only provides new insights into the architecture of MOFs on other MOFs but also develops Z-scheme heterojunction materials for coupling reactions and other organic reactions under visible light irradiation.

A carbon catalyst doped with Co and N derived from the metal-organic framework hybrid (ZIF-8@ZIF-67) for efficient oxygen reduction reaction

Carbon-based catalysts for the oxygen reduction reaction (ORR) are considered potential substitutes for the expensive platinum-based catalysts. Recently, transition metal and nitrogen co-doped carbon materials (M-N-C) have attracted much attention from researchers due to their low cost and excellent activity. A cobalt- and nitrogen-co-doped porous carbon material (Co-N@CNT-C800) was prepared by the simple one-step pyrolysis of a star fruit-like MOF hybrid (ZIF-8@ZIF-67) at 800 °C. It consisted of CNTs with substantial Co and N co-doping and had a large surface area (428 m2·g−1). It had an excellent half-wave potential and good current density in alkaline media in the ORR with values of 0.841 V and 5.07 mA·cm−2, respectively. Compared with commercial Pt/C materials it also had excellent electrochemical stability and methanol tolerance. This research provides an effective way to fabricate low cost, high activity electrocatalysts for use in energy conversion.

Advances of Electroactive Metal-Organic Frameworks.

The preparation of electroactive metal-organic frameworks (MOFs) for applications of supercapacitors and batteries has received much attention and remarkable progress during the past few years. MOF-based materials including pristine MOFs, hybrid MOFs or MOF composites, and MOF derivatives are well designed by a combination of organic linkers (e.g., carboxylic acids, conjugated aromatic phenols/thiols, conjugated aromatic amines, and N-heterocyclic donors) and metal salts to construct predictable structures with appropriate properties. This review will focus on construction strategies of pristine MOFs and hybrid MOFs as anodes, cathodes, separators, and electrolytes in supercapacitors and batteries. Descriptions and discussions follow categories of electrochemical double-layer capacitors (EDLCs), pseudocapacitors (PSCs), and hybrid supercapacitors (HSCs) for supercapacitors. In contrast, Li-ion batteries (LIBs), Lithium-sulfur batteries (LSBs), Lithium-oxygen batteries (LOBs), Sodium-ion batteries (SIBs), Sodium-sulfur batteries (SSBs), Zinc-ion batteries (ZIBs), Zinc-air batteries (ZABs), Aluminum-sulfur batteries (ASBs), and others (e.g., LiSe, NiZn, H+ , alkaline, organic, and redox flow batteries) are categorized for batteries.

Self-supported MOF/cellulose-nanocrystals materials designed from ultrafiltration.

Metal-organic-frameworks (MOFs) are promising materials for addressing critical issues such as petrochemical separation, water purification, energy storage and drug delivery. Their large-scale deployment, however, is hampered by a limited processability due to their powdery nature. Recently, the hybridization of MOFs with biopolymers has emerged as a greener, biocompatible strategy to shape MOFs composites into more processable membranes, films, and porous materials. In this work, cellulose nanocrystals (CNCs) were used in combination with ZIF-8 (a widely used synthetic zeolite) to produce hybrid composites through ultrafiltration. Results showed that small quantities of CNCs (1 to 20 CNC:ZIF-8 volume ratio) were sufficient to form a self-supported, dense deposit with high ZIF-8 loadings. Compared to classical MOF in situ growth strategies, this approach allowed the tuning of the composition of the final nanocomposite by controlling the nature and quantities of particles in the suspension. The fabrication of the deposit was strongly dependent on the physiochemical properties of the suspension, which were fully characterized with a set of complementary techniques, including in situ SAXS. This technique was employed to investigate the filtration process, which exhibited a homogeneous deposition of ZIF-8 particles mediated by CNC self-assembly. Finally, the available pore volume and integrity of the internal porosity of ZIF-8 were characterized by water porosimetry, demonstrating that the presence of CNCs did not alter the properties of the supported ZIF-8.

Pd nanoparticles decorated ultrathin 2D metal-organic framework nanosheets with enhanced peroxidase-mimic activity and colorimetric assay of glucose.

In addition to size, shape and morphology, enzyme-mimetic property could be efficiently regulated by controlling composition, forming complexes or hybrids, and surface modification. Herein, Pd nanoparticles with an average diameter of 2.52 nm were decorated on ultrathin 2D copper(ii)-porphyrin derived metal-organic framework (MOF) nanosheets by a simple reduction method for catalytic activity regulation. In comparison with other nanozymes, the as-synthesized Pd modified 2D MOF hybrid nanosheets (Pd@Cu-TCPP(Fe)) presented excellent peroxidase-mimic activity, exhibiting an even superior catalytic ability towards H2O2 with a Michaelis-Menten constant as low as 2.33 mM. Based on a cascade reaction between glucose oxidase and Pd@Cu-TCPP(Fe), a colorimetric method for the detection of glucose was established and validated with a wide linear range (0.2-8.0 mM), good recovery (89.5-94.2%) and nice reproducibility (3.65%). All these features guaranteed its excellent ability for glucose determination in human cerebrospinal fluids. This study could offer a valuable reference for constructing novel optical biosensors.

Construction of enzyme@glutathione hybrid metal-organic frameworks: glutathione-boosted microenvironment fine-tuning of biomimetic immobilization for improving catalytic performance

Zeolitic imidazolate framework (ZIF) has recently emerged as a promising material for the encapsulation of enzymes because of their high surface area and facile construction conditions. However, the enzymes are partial even completely inactive after encapsulation owing to the confinement effect and competing coordination, and otherwise, the alkaline environment caused by the protonation effect of 2-methylimidazole also damages enzyme molecules. Herein, a novel glutathione (GSH)-boosted one pot embedding strategy that enabled to rapidly encapsulate enzyme within GSH hybrid MOF (named enzyme@GMOF) with a high embedding efficiency was constructed. Hybrid of GSH and imidazole as synchronous ligands for GMOF to immobilize enzyme can offer sufficient well microenvironment for enzyme exhibiting high activity. The obtained catalysts (CAT@GZIF-67) displayed 9.0-fold higher catalytic activity than traditional ZIF-67 immobilized CAT (CAT@ZIF-67) and superior reusability and storage stability compared with CAT@ZIF-67 and free CAT. As one kind of biomacromolecules, bio-affinity of GSH can create an affinitive microenvironment for enzymes and reduce the influence of other factors during the use of biomacromolecules on their conformation and activity.

Highly efficient triiodide ion adsorption from water by ionic liquid hybrid metal–organic frameworks

The development and utilization of nuclear energy is one of the effective ways to reduce carbon emissions and achieve the goal of global carbon neutrality. However, it is inevitable to release radioactive pollutants, such as I3−, into the environment during the utilization of nuclear energy, and the efficient adsorption and storage of iodide ion remains a challenge. In this work, a series of ionic liquid (IL) hybrid metal–organic framework (MOF) materials have been developed by simple impregnation of hydrophobic ILs into nanopores of stable MOFs for high-efficient I3− absorption from water for the first time. It is found that the hybrid materal [C2mim][Tf2N]@UiO-67–30 % exhibits a record high I3− absorption capacity at room temperature (4.30 g·g−1), and the I3− absorption capacity of [C2mim][Tf2N] in UiO-67–5 % is 10 times that of the neat [C2mim][Tf2N]. The adsorption process can be well described by Freundlich model and pseudo-second-order model. Such superior I3− absorption capacity is mainly attributed to the multiple sites interaction between anion of the highly dispersed IL and I3−, although cation of the IL and benzene ring of MOF framework also have contribution for the adsorption.

The Stability of Hybrid Perovskites with UiO-66 Metal-Organic Framework Additives with Heat, Light, and Humidity.

This study is devoted to investigating the stability of metal-organic framework (MOF)-hybrid perovskites consisting of CH3NH3PbI3 (MAPbI3) and UiO-66 without a functional group and UiO-66 with different COOH, NH2,and F functional groups under external influences including heat, light, and humidity. By conducting crystallinity, optical, and X-ray photoelectron spectra (XPS) measurements after long-term aging, all of the prepared MAPbI3@UiO-66 nanocomposites (with pristine UiO-66 or UiO-66 with additional functional groups) were stable to light soaking and a relative humidity (RH) of 50%. Moreover, the UiO-66 and UiO-66-(F)4 hybrid perovskite films possessed a higher heat tolerance than the other two UiO-66 with the additional functional groups of NH2 and COOH. Tthe MAPbI3@UiO-66-(F)4 delivered the highest stability and improved optical properties after aging. This study provides a deeper understanding of the impact of the structure of hybrid MOFs on the stability of the composite films.