Metal Organic Framework Thin Films Research Articles

GIWAXS Characterization of Metal–Organic Framework Thin Films and Heterostructures: Quantifying Structure and Orientation

AbstractFor optoelectronic applications of metal–organic framework (MOF) thin films, it is important to be able to fabricate films and heterostructures that are highly oriented relative to the substrate's surface normal. However, process optimization to achieve this is difficult without sufficiently detailed structural characterization of the deposited films. It is demonstrated that 2D grazing‐incidence wide‐angle X‐ray scattering (GIWAXS) data from a laboratory system go a long way to providing such characterization and can 1) better test structural models than 1D scans, 2) provide a quantitative estimate—useful for process optimization—of the fraction of the deposited film that has the desired surface‐oriented texture (2D powder), and 3) deliver such information as a function of depth into the film—useful for heterostructure characterization. Herein, GIWAXS data collection and analysis are introduced in the context of understanding MOF thin films, then it is shown how the desired oriented fraction (2D powder fraction) of UiO‐66 fabricated by vapor‐assisted conversion can be increased from 4% to over 95% by minimizing nucleation in solution. Finally, it is demonstrated that heterostructures of UiO‐66 and UiO‐67 can be grown wherein both layers are highly ordered (UiO‐66 83%, UiO‐67 >94%) once synthetic protocols are optimized.

Fast Dynamic Synthesis of MIL-68(In) Thin Films in High Optical Quality for Optical Cavity Sensing.

Fabrication of metal-organic framework (MOF) thin films rigidly anchored on suitable substrates is a crucial prerequisite for the integration of these porous hybrid materials into electronic and optical devices. Thus, far, the structural variety for MOF thin films available through layer-by-layer deposition was limited, as the preparation of those surface-anchored metal-organic frameworks (SURMOFs) has several requirements: mild conditions, low temperatures, day-long reaction times, and nonaggressive solvents. We herein present a fast method for the preparation of the MIL SURMOF on Au-surfaces under rather harsh conditions: Using a dynamic layer-by-layer synthesis for MIL-68(In), thin films of adjustable thickness between 50 and 2000 nm could be deposited within only 60 min. The MIL-68(In) thin film growth was monitored in situ using a quartz crystal microbalance. In-plane X-ray diffraction revealed oriented MIL-68(In) growth with the pore-channels of this interesting MOF aligned parallel to the support. Scanning electron microscopy data demonstrated an extraordinarily low roughness of the MIL-68(In) thin films. Mechanical properties and lateral homogeneity of the layer were probed through nanoindentation. These thin films showed extremely high optical quality. By applying a poly(methyl methacrylate) layer and further depositing an Au-mirror to the top, a MOF optical cavity was fabricated that can be used as a Fabry-Perot interferometer. The MIL-68(In)-based cavity showed a series of sharp resonances in the ultraviolet-visible regime. Changes in the refractive index of MIL-68(In) caused by exposure to volatile compounds led to pronounced position shifts of the resonances. Thus, these cavities are well suited to be used as optical read-out sensors.

Layer-by-layer assembly of metal-organic framework thin films: Fabrication and advanced applications

Metal-organic frameworks (MOFs) are a class of crystalline porous coordination materials, which are assembled from inorganic nodes and organic linkers. Numerous applications, such as gas storage, molecule separation, catalysis, optical sensing, and charge transport, benefit from the outstanding properties of MOF materials. More advanced applications, e.g., in the electronics and optoelectronics area, demand homogeneous and monolithic MOF thin films. Recent studies demonstrated that surface-mounted MOFs (SURMOFs) are well suited to fulfill the requirements for the integration of MOFs into devices. As a crystalline thin-film material with tunable thickness, SURMOFs have been widely used in the optimization of chromophore stacking, electrical transport, stimuli-response, etc. The fabrication of SURMOFs is carried out employing a layer-by-layer (LbL) assembly technique, and it can yield MOF thin films with a well-defined orientation, tunable thickness, and editable crystalline heterostructure. We summarize the LbL assembly methods for SURMOF fabrication and the realization of advanced SURMOF architectures, including optical and electronic applications as well as the integration of photoactive SURMOFs and SURMOF-derived materials in technical devices. We conclude with a discussion of the challenges and prediction of the future of SURMOF materials.

Building metal-organic framework thin films for advanced optic, electronic applications

Thin films made from metal-organic frameworks offer unique properties and useful characteristics with low-cost layer-by-layer fabrication.

In Situ Fabrication of Metal–Organic Framework Thin Films with Enhanced Pervaporation Performance

AbstractThe intrinsic porosity in the periodic structures of metal–organic frameworks (MOFs) endows them with a great potential for membrane separation. However, facile fabrication of crystalline MOF membranes has been challenging and limited to few materials for economic and environmental considerations. Herein, a continuous Zr‐MOF thin film with a thickness of ≈180 nm has been fabricated via in situ recrystallization of MOF nanoparticles on the porous support under formic acid vapor. Owing to the inherent microporosity and the well‐established hydrophilicity during membrane fabrication, the MOF thin films exhibit excellent pervaporation performance with separation factors of 2630, 501 and fluxes of 1.45, 1.41 kg m−2 h−1) for n‐butanol dehydration and methanol/methyl tert‐butyl ether (MeOH/MTBE) separation, respectively. The structural stability of the film has been further confirmed by its steady performance in the 10‐day pervaporation test. This in situ recrystallization method induced by a trace amount of acid vapor with no extra ingredients opens a new avenue for the facile membrane fabrication of various MOF materials to feasibly realize their versatile potential as membrane materials.

In Operando Spectroscopic Ellipsometry Investigation of MOF Thin Films for the Selective Capture of Acetic Acid.

The emission of polar volatile organic compounds (VOCs) is a major worldwide concern of air quality and equally impacts the preservation of cultural heritage (CH). The challenge is to design highly efficient adsorbents able to selectively capture traces of VOCs such as acetic acid (AA) in the presence of relative humidity (RH) normally found at storage in museums (40-80%). Although the selective capture of VOCs over water is still challenging, metal-organic frameworks (MOFs) possess highly tunable features (Lewis, Bronsted, or redox metal sites, functional groups, hydrophobicity, etc.) suitable to selectively capture a large variety of VOCs. In this context, we have explored the adsorption efficiency of a series of MOFs thin films (ZIF-8(Zn), MIL-101(Cr), and UiO-66(Zr)-2CF3) for the selective capture of AA based on a UV/vis and FT-IR spectroscopic ellipsometry in operando study (2-6% of relative pressure of AA under 40% of RH), namely conditions close to the realistic environmental storage conditions of cultural artifacts. For that purpose, optical quality thin films of MOFs were prepared by dip-coating, and their AA adsorption capacity and selectivity were evaluated under humid conditions by measuring the variation of the refractive index as a function of the vapor pressures while the chemical nature of the coadsorbed analytes (water and AA) was identified by FT-IR ellipsometry. While thin films of ZIF-8(Zn) strongly degraded upon exposure to AA/water vapors, films of MIL-101(Cr) and UiO-66(Zr)-2CF3 present a high chemical stability under those conditions. It was shown that MIL-101(Cr) presents a high AA adsorption capacity due to its high pore volume but exhibits a poor AA adsorption selectivity under humid conditions. In contrast, UiO-66(Zr)-2CF3 was shown to overpass MIL-101(Cr) in terms of AA/H2O adsorption selectivity and AA adsorption/desorption cycling stability because of its high hydrophobic character, suitable pore size for adequate confinement, and specific interactions.

Reversible Regulation of Polar Gas Molecules by Azobenzene-Based Photoswitchable Metal-Organic Framework Thin Films.

The development of tunable molecule separation membranes requires materials with remote controllability and ultra-high separation capability. In this paper, a novel photoswitchable metal organic framework (MOF) thin film (Cu2(AzoBPDC)2) was prepared by liquid phase epitaxial layer-by-layer assembly to realize the reversible remote-controlled switching. The azobenzene side groups in the Cu2(AzoBPDC)2 thin film showed excellent reversible photoswitching performance under UV (365 nm) and Vis (450 nm) irradiation, achieving the remote-controlled mode of the diffusion flux of polar gas molecules in the MOF thin film.

Synthesis of UiO-66-Sal-Cu(OH)2 by a Simple and Novel Method: MOF-Based Metal Thin Film as a Heterogeneous Catalyst for Olefin Oxidation

Metal-organic frameworks (MOFs), particularly UiO-66-NH2, are employed as a catalyst in many industrial catalyst applications. As converting catalysts into thin film significantly increases their catalytic properties for the epoxidation of olefins, we report a general approach to synthesizing MOF thin films (UiO-66-Sal-Cu(OH)2). Using the postsynthesis method (PSM), UiO-66-NH2 was functionalized with salicylaldehyde and entrapped on copper hydroxide nanoparticle surfaces using a modern strategy (MOF thin film). We used field-emission scanning electron microscopy (FE-SEM), EDX (energy-dispersive X-ray analysis), XRD (X-ray diffraction), FT-IR (Fourier transform infrared), BET (Brunauer-Emmett-Teller), TGA (thermogravimetric analysis), XPS (X-ray photoelectron spectroscopy), and ICP-MS (inductively coupled plasma mass spectrometry) to determine the structure and morphology of the synthesized UiO-66-Sal-Cu(OH)2. The oxidation of cyclooctene by the UiO-66-Sal-Cu(OH)2 thin film was studied. Due to its advantages, such as being environmentally friendly (base metal-loaded catalyst, room temperature, solvent-free reaction), reusability, and high yield, this compound can be an appropriate catalyst for the oxidation of olefins.

Nanoporous Metal-Organic Framework Thin Films Prepared Directly from Gaseous Precursors by Atomic and Molecular Layer Deposition: Implications for Microelectronics.

Atomic/molecular layer deposition (ALD/MLD) allows for the direct gas-phase synthesis of crystalline metal-organic framework (MOF) thin films. Here, we show for the first time using krypton and methanol physisorption measurements that ALD/MLD-fabricated copper 1,4-benzenedicarboxylate (Cu-BDC) ultrathin films possess accessible porosity matching that of the corresponding bulk MOF.

Investigating the vapour phase synthesis of copper terephthalate metal organic framework thin films by atomic/molecular layer deposition.

Solventless synthesis and processing of Metal Organic Frameworks (MOFs) is critical to implement these materials in applied technologies. Vapour phase synthesis of MOF thin films is particularly suitable for such applications, but challenging compared to the conventional solution based methods. It is therefore compelling to advance and widen the vapour phase synthesis of MOF thin films. Crystalline copper terephthalate MOF thin films are grown in the vapour phase by means of atomic and molecular layer deposition (ALD/MLD) on different kinds of substrates. Expanding from the pioneering work, the formation of the 3D phase is clearly evidenced for the first time and the adaptability of the process to several kinds of substrates is revealed. A directional film growth is observed at the early stage of the ALD/MLD process leading to oriented MOF crystallites on a surface, when isotropical growth proceeds with the increasing number of ALD/MLD cycles. Notably, this study primarily demonstrates a heteroepitaxial growth achievable in the vapour phase by using DMOF-1 single crystals as the starting surface with a lattice matching topology. Such an approach offers an appealing pathway to develop MOF on MOF superlattice materials in the vapour phase.

Liquid-phase epitaxial growth of multiple MOF thin films with high lattice mismatch

We have prepared a series of multiple (bi-varietal and tri-varietal) pillar-layered MOF thin films [Cu2L2dabco]n (L = bdc, bpc and tpdc) with high lattice mismatch (up to 77.8%) using a liquid-phase epitaxial layer by layer method.

Polarization-dependent plasmonic heating in epitaxially grown multilayered metal-organic framework thin films embedded with Ag nanoparticles.

The development of metal-organic framework (MOF) thin films with various functionalities has paved the way for research into a wide variety of applications. MOF-oriented thin films can exhibit anisotropic functionality in the not only out-of-plane but also in-plane directions, making it possible to utilize MOF thin films for more sophisticated applications. However, the functionality of oriented MOF thin films has not been fully exploited, and finding novel anisotropic functionality in oriented MOF thin films should be cultivated. In the present study, we report the first demonstration of polarization-dependent plasmonic heating in a MOF oriented film embedded with Ag nanoparticles (AgNPs), pioneering an anisotropic optical functionality in MOF thin films. Spherical AgNPs exhibit polarization-dependent plasmon-resonance absorption (anisotropic plasmon damping) when incorporated into an anisotropic lattice of MOFs. The anisotropic plasmon resonance results in a polarization-dependent plasmonic heating behavior; the highest elevated temperature was observed in case the polarization of incident light is parallel to the crystallographic axis of the host MOF lattice favorable for the larger plasmon resonance, resulting in polarization-controlled temperature regulation. Such spatially and polarization selective plasmonic heating offered by the use of oriented MOF thin films as a host can pave the way for applications such as efficient reactivation in MOF thin film sensors, partial catalytic reactions in MOF thin film devices, and soft microrobotics in composites with thermo-responsive materials.

Tunable J-type aggregation of silicon phthalocyanines in a surface-anchored metal-organic framework thin film.

Organic chromophores and semiconductors, like anthracene, pentacene, perylene, and porphyrin, are prone to aggregation, and their packing in the solid state is often hard to predict and difficult to control. As the condensed phase structures of these chromophores and semiconductors are of crucial importance for their optoelectronic functionality, strategies to control their assembly and provide new structural motifs are important. One such approach uses metal-organic frameworks (MOFs); the organic chromophore is converted into a linker and connected by metal ions or nodes. The spatial arrangement of the organic linkers can be well-defined in a MOF, and hence optoelectronic functions can be adjusted accordingly. We have used such a strategy to assemble a phthalocyanine chromophore and illustrated that the electronic inter-phthalocyanine coupling can be rationally tuned by introducing bulky side grounds to increase steric hindrance. We have designed new phthalocyanine linkers and using a layer-by-layer liquid-phase epitaxy strategy thin films of phthalocyanine-based MOFs have been fabricated and their photophysical properties explored. It was found that increasing the steric hindrance around the phthalocyanine reduced the effect of J-aggregation in the thin film structures.

Elucidating polymer growth and fragmentation behavior of MOFs in ethylene polymerization by MOF thin films

Elucidating polymer growth and fragmentation behavior of MOFs in ethylene polymerization by MOF thin films

Nanoporous Films with Oriented Arrays of Molecular Motors for Photoswitching the Guest Adsorption and Diffusion.

Molecular motors are fascinating nanomachines. However, constructing smart materials from such functional molecules presents a severe challenge in material science. Here, we present a bottom-up layer-by-layer assembly of oriented overcrowded-alkene molecular motors forming a crystalline metal-organic framework thin film. While all stator parts of the overcrowded-alkene motors are oriented perpendicular to the substrate, the rotors point into the pores, which are large enough allowing for the light-induced molecular rotation. Taking advantage of the thin film's transparency, the motor rotation and its activation energy are determined by UV/Vis spectroscopy. As shown by gravimetric uptake experiments, molecular motors in crystalline porous materials are used, for the first time, to control the adsorption and diffusion properties of guest molecules in the pores, here, by switching with light between the (meta-)stable states. The work demonstrates the potential of designed materials with molecular motors and indicates a path for the future development of smart materials.

Coupling tandem MOFs in metal-insulator-metal resonator advanced chemo-sieving sensing

Metal-insulator-metal (MIM) resonator allows concentrating light into deep-subwavelength volumes for filtering by accessing surface plasmon polariton mode, which is typically constructed by using inorganic materials and polymers as an insulator. Although MIM filters can manipulate light, dynamic color change upon environmental stimuli is still challenging. Here, we report a metal-organic frameworks (MOFs) based MIM resonator with tunable bandwidth that can realize visualized sensing of chemicals. Different bandwidths of the resonator show distinct color reflection that can be tailored by different types of MOFs and thickness of the MOFs layers. Chemical sensing on the MOFs-based MIM resonators shows breakthrough enhancement of sensitivity. Moreover, we configure tandem MOFs thin films in the MIM to form a metal-insulator-insulator-metal (MIIM) resonator for promoting selective sensing of chemicals. Also, molecular dynamics simulations demonstrated that the MIIM resonator achieved selective adsorption of xylenes in a mixture of xylene and methanol due to the chemo-sieving effect. The MIIM resonators show not only host-guest chemistry and sieving performance of tandem MOFs with high durability, but also anti-interference selective sensing of analyte in the mixture.

PH-Responsive Metal-Organic Framework Thin Film for Drug Delivery.

In this work, surface-supportive MIL-88B(Fe) was explored as a pH-stimuli thin film to release ibuprofen as a model drug. We used surface plasmon resonance microscopy to study the pH-responsive behaviors of MIL-88B(Fe) film in real time. A dissociation constant of (6.10 ± 0.86) × 10-3 s-1 was measured for the MIL-88B(Fe) film in an acidic condition (pH 6.3), which is about 10 times higher than the dissociation of the same film in a neutral pH condition. MIL-88B(Fe) films are also capable of loading around 6.0 μg/cm2 of ibuprofen, which was measured using a quartz crystal microbalance (QCM). Drug release profiles were compared in both acidic and neutral pH conditions (pH 6.3 and 7.4) using a QCM cell to model the drug release in healthy body systems and those containing inflammatory tissues or cancerous tumors. It was found that the amount of drug released in acidic environments had been significantly higher compared to that in a neutral system within 55 h of testing time. The pH-sensitive chemical bond breaking between Fe3+ and the carboxylate ligands is the leading cause of drug release in acidic conditions. This work exhibits the potential of using MOF thin films as pH-triggered drug delivery systems.

Charge-transfer interface of insulating metal-organic frameworks with metallic conduction

Downsizing materials into hetero-structured thin film configurations is an important avenue to capture various interfacial phenomena. Metallic conduction at the interfaces of insulating transition metal oxides and organic molecules are notable examples, though, it remained elusive in the domain of coordination polymers including metal-organic frameworks (MOFs). MOFs are comprised of metal centers connected to organic linkers with an extended coordination geometry and potential void space. Poor orbitals overlap often makes these crystalline solids electrical insulators. Herein, we have fabricated hetero-structured thin film of a Mott and a band insulating MOFs via layer-by-layer method. Electrical transport measurements across the thin film evidenced an interfacial metallic conduction. The origin of such an unusual observation was understood by the first-principles density functional theory calculations; specifically, Bader charge analysis revealed significant accumulation and percolation of charge across the interface. We anticipate similar interfacial effects in other rationally designed hetero-structured thin films of MOFs.

Photoresponsive Polymer and Polymer Composite Membranes for Gas Separation

Stimuli-responsive materials, referred to as “smart” or “intelligent” materials, have gained significant attention in the separation fields, including gas separation. Among a variety of available stimuli, the use of light as a nondestructive, cost-efficient, chemical-reagent-free stimulus with a relatively fast response is very promising. Herein, we summarize and highlight the approaches applied for the synthesis of photoresponsive organic polymeric membranes, inorganic metal–organic framework thin films, and inorganic–organic mixed-matrix membranes. We discuss the application of these materials for gas separation and provide selected state-of-the-art examples from recently conducted studies. Additionally, the photoresponsive gas separation membrane testing cell plays a crucial role in evaluating and comparing the performance of photoresponsive membranes in the gas separation process. Therefore, we review the development of photoresponsive gas separation membrane testing cells along with the ascribed drawbacks and limitations. A third generation testing system designed to highlight test accuracy is proposed and discussed.

Fully Automated Optimization of Robot‐Based MOF Thin Film Growth via Machine Learning Approaches

AbstractMetal–organic frameworks (MOFs), have emerged as ideal class of materials for the identification of structure–property relationships and for the targeted design of multifunctional materials for diverse applications. While the powder form is most common, for the integration of MOFs into devices, typically thin films of surface anchored MOFs (SURMOFs), are required. Although the quality of SURMOFs emerging from layer‐by‐layer approaches is impressive, previous works revealed that the optimum growth conditions are very different between different types of MOFs and different substrates. Furthermore, the choice of appropriate synthesis conditions (e.g., solvents, modulators, concentrations, immersion times) is crucial for the growth process and needs to be adjusted for different substrates. Machine learning (ML) approaches show great promise for multi‐parameter optimization problems such as the above discussed growth conditions for SURMOF on a particular substrate. Here, this work presents an ML‐based approach allowing to quickly identify optimized growth conditions for HKUST‐I SURMOFs with high crystallinity and uniform orientation. This process can subsequently be used to optimize growth on other types of substrates. In addition, an analysis of the results allows to gain further insights into the factors governing the growth of MOF thin films.