Surface-mounted Metal-organic Frameworks Research Articles

Classification and Identification of Perfume Scents by an Enantioselective Colorimetric Sensor Array of Chiral Metal-Organic-Framework-Based Fabry-Pérot Films.

Many odors, like perfumes, are complex mixtures of chiral and achiral molecules where the cost-efficient (enantio-)selective sensing represents a major technical challenge. Here, we present a colorimetric sensor array of surface-mounted metal-organic-framework (SURMOF) films in Fabry-Pérot (FP) cavities. The optical properties of the FP-SURMOF films with different chiral and achiral structures are affected by the (enantio-)selective adsorption of the analytes in the SURMOF pores, resulting in different responses to the analyte molecules. The read-out of the sensor array is performed by the digital camera of a common smartphone, where the RGB values are determined. By analyzing the sensor array data with simple machine learning algorithms, the analytes are discriminated. After demonstrating the enantioselective response for a pair of pure chiral odor molecules, we apply the sensor array to detect and discriminate a large number (16) of common commercial perfumes and eau de toilettes. While our untrained human nose is not able to discriminate all perfumes, the presented colorimetric sensor array can classify all perfumes with great classification accuracy. Moreover, the sensor array was used to identify unlabeled samples correctly. We foresee such an FP-chiral-SURMOF-based sensor array as a powerful approach toward inexpensive selective odors sensing applications.

Dünne Schichten metallorganischer Gerüstverbindungen als ideale Matrizes für die Azid‐Photolyse im Vakuum

AbstractStudien zu Reaktionen in Lösungen werden oft durch Lösungsmitteleffekte behindert. Zudem ist eine detaillierte Untersuchung der Kinetik auf den kleinen Temperaturbereich beschränkt, in dem das Lösungsmittel flüssig ist. Hier berichten wir über die spektroskopische in situ‐Beobachtung UV‐induzierter Reaktionen von Arylaziden in einer kristallinen Matrix im Vakuum. Die Matrizes werden durch Bindung der reaktiven Teile an ditopische Linker, die dann zu metallorganischen Gerüstverbindungen (MOFs) und oberflächenverankerten MOFs (SURMOFs) zusammengesetzt werden, gebildet. Diese porösen, kristallinen Gerüstverbindungen werden dann als Modellsysteme verwendet, um die chemischen Prozesse im Zusammenhang mit Aziden unter Ultrahochvakuum(UHV)‐Bedingungen – bei denen Lösungsmitteleffekte sicher ausgeschlossen werden können – und in einem großen Temperaturbereich zu untersuchen. Die Infrarot‐Reflexions‐Absorptions‐Spektroskopie (IRRAS) ermöglichte es uns, die Photoreaktion von Aziden in SURMOFs präzise zu überwachen. Die in situ‐IRRAS‐Daten zeigten in Verbindung mit XRD, MS und XPS, dass die Bestrahlung mit UV‐Licht zunächst zur Bildung eines Nitren‐Zwischenprodukts führt. Im zweiten Schritt findet eine intramolekulare Umlagerung statt, die ein Indoloindol‐Derivat ergibt. Diese Ergebnisse eröffnen einen neuartigen Weg für die präzise Untersuchung von chemischen Umwandlungen von Aziden. Referenzexperimente, die für lösungsmittelbeladene SURMOFs durchgeführt wurden, offenbaren eine enorme Vielfalt anderer Reaktionsschemata und unterstreichen daher den Bedarf an Modellsystemen, die unter UHV‐Bedingungen untersucht werden.

Metal-Organic Framework Thin Films as Ideal Matrices for Azide Photolysis in Vacuum.

Studies on reactions in solutions are often hampered by solvent effects. In addition, detailed investigation on kinetics is limited to the small temperature regime where the solvent is liquid. Here, we report the in situ spectroscopic observation of UV-induced photochemical reactions of aryl azides within a crystalline matrix in vacuum. The matrices are formed by attaching the reactive moieties to ditopic linkers, which are then assembled to yield metal-organic frameworks (MOFs) and surface-mounted MOFs (SURMOFs). These porous, crystalline frameworks are then used as model systems to study azide-related chemical processes under ultrahigh vacuum (UHV) conditions, where solvent effects can be safely excluded and in a large temperature regime. Infrared reflection absorption spectroscopy (IRRAS) allowed us to monitor the photoreaction of azide in SURMOFs precisely. The in situ IRRAS data, in conjunction with XRD, MS, and XPS, reveal that illumination with UV light first leads to forming a nitrene intermediate. In the second step, an intramolecular rearrangement occurs, yielding an indoloindole derivative. These findings unveil a novel pathway for precisely studying azide-related chemical transformations. Reference experiments carried out for solvent-loaded SURMOFs reveal a huge diversity of other reaction schemes, thus highlighting the need for model systems studied under UHV conditions.

Optical sensor array of metal-organic-framework-based inverse opal films for the detection and identification of various alcohols

Reliable and inexpensive sensors for the detection and discrimination of various volatile organic compounds like different alcohols are required for many applications, for example to proof the alcohol quality and for avoiding methanol poising. Here, we develop a sensor array of films made of different types of surface-mounted metal-organic frameworks (SURMOFs) with a periodic three-dimensional structure of mesoscopic voids, referred to as inverse opal structure. The wavelength shift (or alternatively, the intensity change) of the photonic reflectance peak caused by the analyte vapor adsorption in the SURMOF was used as signal. The sensor array is applied for the detection of various pure low-carbon alcohols, which are methanol, ethanol, 1-propanol, and 1-butanol. The sensor array shows a low limit of detection (LOD) in the range of 10–60 ppm and is able to reliably discriminate the alcohols from each other. Furthermore, the sensor array is able to precisely discriminate their pure vapors and binary mixtures with methanol. We foresee such sensor array with SURMOF-based inverse opal films offer a great potential for the precise and cost-efficient detection of various analytes.

Substrate-Bound Diarylethene-Based Anisotropic Metal-Organic Framework Films as Photoactuators with a Directed Response.

Molecular machines and responsive materials open a plethora of new opportunities in nanotechnology. We present an oriented crystalline array of diarylethene (DAE)-based photoactuators, arranged in a way to yield an anisotropic response. The DAE units are assembled, together with a secondary linker, into a monolithic surface-mounted metal-organic framework (SURMOF) film. By Infrared (IR) and UV/Vis spectroscopy as well as by synchrotron X-ray diffraction, we show that the light-induced extension changes of the molecular DAE linkers multiply to yield mesoscopic and anisotropic length changes. Due to the special architecture and substrate-bonding of the SURMOF, these length changes are transferred to the macroscopic scale, leading to the bending of a cantilever and performing work. This research shows the potential of assembling light-powered molecules into SURMOFs to yield photoactuators with a directed response, presenting a path to advanced actuators.

Formation of Gold Nanoclusters from Goldcarbonyl Chloride inside the Metal-Organic Framework HKUST-1

Gas-phase infiltration of the carbonylchloridogold(I), Au(CO)Cl precursor into the pores of HKUST-1 ([Cu3(BTC)2(H2O)2], Cu-BTC) SURMOFs (surface-mounted metal-organic frameworks; BTC = benzene-1,3,5-tricarboxylate) leads to Au(CO)Cl decomposition within the MOF through hydrolysis with the aqua ligands on Cu. Small Aux clusters with an average atom number of x ≈ 5 are formed in the medium-sized pores of the HKUST-1 matrix. These gold nanoclusters are homogeneously distributed and crystallographically ordered, which was supported by simulations of the powder X-ray diffractometric characterization. Aux@HKUST-1 was further characterized by scanning electron microscopy (SEM) and infrared reflection absorption (IRRA) as well as Raman spectroscopy, time-of-flight secondary ion mass spectrometry (ToF-SIMS), X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma optical emission spectroscopy (ICP-OES).

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.

Optical sensor array of chiral MOF-based Fabry-Pérot films for enantioselective odor sensing.

An optical sensor array based on photonic Fabry-Pérot films of surface-mounted metal-organic-frameworks (SURMOFs) with different homochiral structures is presented. It is used to detect and enantioselectively discriminant 3 pairs of chiral odor molecules, either pure or in binary mixtures.

A binder-free, well-integrated metal–organic frameworks@polypyrrole nanofilm electrocatalyst for highly efficient and selective reduction of carbon dioxide

Metal–organic frameworks (MOFs) are promising electrocatalysts for carbon dioxide reduction reaction (CO2RR) due to their designable crystalline structures, large surface area, and atomically dispersed active sites. However, the poor electric conductivity of MOFs, leading to the low utilization of large amounts of active sites, greatly inhibits their practical applications in electrocatalysis. Herein, a binder-free, MOF-based nanofilm electrocatalyst for highly efficient and selective CO2RR is achieved by well-grafting conductive polypyrrole (PPy) chains into surface-mounted MOF (ZIF-8) nanofilm electrocatalyst based on a combination of the layer-by-layer assembly MOF growth technique and the in-situ electrochemical polymerization method. Experimental and theoretical results confirm that the grafting of PPy not only significantly accelerates the electron transfer for high utilization of active sites but also optimizes the electronic structure of the electrocatalysts for high electrocatalytic activity. As a result, the optimized ZIF-8@PPy nanofilm electrocatalyst exhibits the excellent electrocatalytic CO2RR performance with a selectivity of 96% and a current density of up to 18 mA/cm2 at −1.1 V. The strategy in this work has also demonstrated the broad potential application to a variety of other electrochemical purposes.

Epitaxial Growth of Guanidyl-Functionalized Magnetic Metal-Organic Frameworks with Multiaffinity Sites for Selective Capture of Global Phosphopeptides.

The flexible and controlled synthesis of metal-organic framework (MOF)-derived hybrid nanostructures is of great significance in fine tuning of their enrichment performance in large-scale and in-depth phosphoproteome analysis. Herein, a magnetic guanidyl-functionalized MOF hybrid coating with multiaffinity sites, denoted as Fe3O4@G-ZIF-8, was fast fabricated via a one-pot epitaxial growth strategy for the first time and applied for selective and highly efficient enrichment of global phosphopeptides. The intrinsic unsaturated metal sites of ZIF-8 endow the surface-mounted MOF coatings with immobilized metal ion affinity chromatography interaction with multiphosphorylated peptides. The oriented anchoring of bifunctional guanidineacetic acid on the magnetic MOF nanospheres provides additional affinity sites (guanidyl groups) for specific recognition of phosphopeptides by "salt bridge" interaction, as well as active site carboxyl groups for the coordination with the metal ions. The as-prepared Fe3O4@G-ZIF-8 exhibits large surface area (382.5 m2 g-1), good superparamagnetic property (41.6 emu g-1) and stability, and size-exclusion effect (1.73 nm), which can serve as a specific adsorbent for global phosphopeptide analysis with satisfactory selectivity, great detection sensitivity (1 fmol), and rapid magnetic separation. Moreover, the successful application of Fe3O4@G-ZIF-8 for selective capture of both multi- and mono-phosphopeptides from human saliva and serum demonstrated the great potential of magnetic surface-mounted MOF coatings in effective identification of low-abundance phosphopeptides by matrix-assisted laser desorption ionization time-of-flight mass spectrometry from complicated biological matrices.

Dual In Situ Laser Techniques Underpin the Role of Cations in Impacting Electrocatalysts.

Understanding the electrode/electrolyte interface is crucial for optimizing electrocatalytic performances. Here, we demonstrate that the nature of alkali metal cations can profoundly impact the oxygen evolution activity of surface‐mounted metal–organic framework (SURMOF) derived electrocatalysts, which are based on NiFe(OOH). In situ Raman spectroscopy results show that Raman shifts of the Ni−O bending vibration are inversely proportional to the mass activities from Cs+ to Li+. Particularly, a laser‐induced current transient technique was introduced to study the cation‐dependent electric double layer properties and their effects on the activity. The catalytic trend appeared to be closely related to the potential of maximum entropy of the system, suggesting a strong cation impact on the interfacial water layer structure. Our results highlight how the electrolyte composition can be used to maximize the performance of SURMOF derivatives toward electrochemical water splitting.

Dual In Situ Laser Techniques Underpin the Role of Cations in Impacting Electrocatalysts

AbstractUnderstanding the electrode/electrolyte interface is crucial for optimizing electrocatalytic performances. Here, we demonstrate that the nature of alkali metal cations can profoundly impact the oxygen evolution activity of surface‐mounted metal–organic framework (SURMOF) derived electrocatalysts, which are based on NiFe(OOH). In situ Raman spectroscopy results show that Raman shifts of the Ni−O bending vibration are inversely proportional to the mass activities from Cs+ to Li+. Particularly, a laser‐induced current transient technique was introduced to study the cation‐dependent electric double layer properties and their effects on the activity. The catalytic trend appeared to be closely related to the potential of maximum entropy of the system, suggesting a strong cation impact on the interfacial water layer structure. Our results highlight how the electrolyte composition can be used to maximize the performance of SURMOF derivatives toward electrochemical water splitting.

Sensing Molecules with Metal-Organic Framework Functionalized Graphene Transistors.

Graphene is inherently sensitive to vicinal dielectrics and local charge distributions, a property that can be probed by the position of the Dirac point in graphene field-effect transistors. Exploiting this as a useful sensing principle requires selectivity; however, graphene itself exhibits no molecule-specific interaction. Complementarily, metal-organic frameworks can be tailored to selective adsorption of specific molecular species. Here, a selective ethanol sensor is demonstrated by growing a surface-mounted metal-organic framework (SURMOF) directly onto graphene field-effect transistors (GFETs). Unprecedented shifts of the Dirac point, as large as 15V, are observed when the SURMOF/GFET is exposed to ethanol, while a vanishingly small response is observed for isopropanol, methanol, and other constituents of the air, including water. The synthesis and conditioning of the hybrid materials sensor with its functional characteristics are described and a model is proposed to explain the origin, magnitude, and direction of the Dirac point voltage shift. Tailoring multiple SURMOFs to adsorb specific gases on an array of such devices thus generates a versatile, selective, and highly sensitive platform for sensing applications.

Metamorphosis of Heterostructured Surface-Mounted Metal-Organic Frameworks Yielding Record Oxygen Evolution Mass Activities.

Materials derived from surface-mounted metal-organic frameworks (SURMOFs) are promising electrocatalysts for the oxygen evolution reaction (OER). A series of mixed-metal, heterostructured SURMOFs is fabricated by the facile layer-by-layer deposition method. The obtained materials reveal record-high electrocatalyst mass activities of ≈2.90 kA g-1 at an overpotential of 300mV in 0.1 m KOH, superior to the benchmarking precious and nonprecious metal electrocatalysts. This property is assigned to the particular in situ self-reconstruction and self-activation of the SURMOFs during the immersion and the electrochemical treatment in alkaline aqueous electrolytes, which allows for the generation of NiFe (oxy)hydroxide electrocatalyst materials of specific morphology and microstructure.

Surface-Mounted Metal-Organic Frameworks: Past, Present, and Future Perspectives.

Metal-organic frameworks (MOFs) are an emerging class of porous materials composed of organic linkers and metal centers/clusters. The integration of MOFs onto the solid surface as thin films/coatings has spurred great interest, thanks to leveraging control over their morphology (such as size- and shape-regulated crystals) and orientation, flexible processability, and easy recyclability. These aspects, in synergy, promise a wide range of applications, including but not limited to gas/liquid separations, chemical sensing, and electronics. Dozens of innovative methods have been developed to manipulate MOFs on various solid substrates for academic studies and potential industrial applications. Among the developed deposition methods, the liquid-phase epitaxial layer-by-layer (LPE-LbL) method has demonstrated its merits over precise control of the thickness, roughness, homogeneity, and orientations, among others. Herein, we discuss the major developments of surface-mounted MOFs (SURMOFs) in LbL process optimization, summarizing the SURMOFs' performance in different applications, and put forward our perspective on the future of SURMOFs in terms of advances in the formulation, applications, and challenges. Finally, future prospects and challenges with respect to SURMOFs growth will be discussed, keeping the focus on their widening applications.

In Situ Tracking of Wetting-Front Transient Heat Release on a Surface-Mounted Metal-Organic Framework.

Transient heat generation during guest adsorption and host-guest interactions is a natural phenomenon in metal-organic framework (MOF) chemistry. However, in situ tracking of such MOF released heat is an insufficiently researched field due to the fast heat dissipation to the surroundings. Herein, a facile capillary-driven liquid-imbibition approach is developed for in situ tracking of transient heat release at the wetting front of surface-mounted MOFs (SURMOFs) on cellulosic fiber substrates. Spatiotemporal temperature distributions are obtained with infrared thermal imaging for a range of MOF-based substrates and imbibed liquids. Temperature rises at the wetting front of water and binary mixtures with organic solvents are found to be over 10K with an ultrafast and distinguishable thermal signal response (<1 s) with a detectable concentration limit ≤1 wt%. As an advancement to the state-of-the-art in trace-solvent detection technologies, this study shows great prospects for the integration of SURMOFs in future sensor devices. Inspired by this prototypal study, SURMOF-based transient heat signal transduction is likely to be extended to an ever-expanding library of SURMOFs and other classes of surface-grafted porous materials, translating into a wide range of convenient, portable, and ubiquitous sensor devices.

Halogenated Terephthalic Acid "Antenna Effects" in Lanthanide-SURMOF Thin Films.

Lanthanide-based crystalline coatings have a great potential for energy-conversion devices, but until now luminescent surface-anchored materials were difficult to fabricate. Thin films, called lanthanides surface-mounted metal-organic frameworks (SURMOFs) with tetrasubstituted halide (fluorine, chlorine, and bromine) terephthalic acid derivative linkers as a basic platform for optical devices, exhibit a high quantum yield of fluorescence visible to the naked eyes under ambient light. We show that we can tune the luminescent properties in thin films by halide substitution, which affords control over the molecular structure of the material. We rationalize the mechanism for the modulation of the photophysical properties by "antenna effect", which controls the energy transfer and quantum yields using experimental and theoretical techniques for chelated lanthanides as a function of the type of atom substitutions at the phenyl rings and the resulting dihedral angle between phenyl rings in the linkers and carboxylate groups.

In Situ Spectroscopy of Calcium Fluoride Anchored Metal-Organic Framework Thin Films during Gas Sorption.

Surface‐mounted metal–organic frameworks (SURMOFs) show promising behavior for a manifold of applications. As MOF thin films are often unsuitable for conventional characterization techniques, understanding their advantageous properties over their bulk counterparts presents a great analytical challenge. In this work, we demonstrate that MOFs can be grown on calcium fluoride (CaF2) windows after proper functionalization. As CaF2 is optically (in the IR and UV/Vis range of the spectrum) transparent, this makes it possible to study SURMOFs using conventional spectroscopic tools typically used during catalysis or gas sorption. Hence, we have measured HKUST‐1 during the adsorption of CO and NO. We show that no copper oxide impurities are observed and also confirm that SURMOFs grown by a layer‐by‐layer (LbL) approach possess Cu+ species in paddlewheel confirmation, but 1.9 times less than in bulk HKUST‐1. The developed methodology paves the way for studying the interaction of any adsorbed gases with thin films, not limited to MOFs, low temperatures, or these specific probe molecules, pushing the boundaries of our current understanding of functional porous materials.

Studying ZIF-8 SURMOF Thin Films with a Langatate Crystal Microbalance: Single-Component Gas Adsorption Isotherms Measured at Elevated Temperatures and Pressures.

Characterizing the adsorption behavior of thin films at technical operation ranges is highly relevant in order to obtain appropriate experimental parameters, as well as to evaluate their possible integration in multiple applications. Nonetheless, gathering such experimental data is not a trivial task. In the case of metal-organic framework thin films, a particular interesting class of highly porous coatings, determination of adsorption isotherms at elevated temperatures and pressures is not commonly reported. Using a custom-designed langatate crystal microbalance following the principle for piezoelectric microbalances, but under harsher conditions, allowed us to present adsorption equilibrium measurements on a zeolitic imidazolate framework-8 (ZIF-8) surface-mounted metal-organic framework (SURMOF) thin film at temperatures between 35 and 100 °C and at a pressure range up to 10 bars. The layer-by-layer liquid-phase epitaxy approach was used to deposit ZIF-8 SURMOF thin films on langatate crystals. X-ray diffraction, infrared reflection absorption spectroscopy, and scanning electron microscopy combined with energy dispersive X-ray mapping were used to gather deeper information on the ZIF-8 thin film growth. Single-component isotherms were collected for different gases of practical interest, that is, CO2, C2H6, C2H4, C3H8, and C3H6. The measurements were obtained at 35, 50, 75, and 100 °C at a gauge pressure range up to 10 bars. The collected data showed a clear preferential adsorption of ethane over ethylene, whereas only a slight difference was found between propane and propylene. Additionally, the experimental data allowed for the determination of adsorption equilibrium constants and saturation loadings of the ZIF-8 material as a thin SURMOF film, which is of great importance for its integration in multiple applications, such as sensor devices or in membrane-based separation.

Conductive Metal-Organic Framework Thin Film Hybrids by Electropolymerization of Monosubstituted Acetylenes.

1-Hexyne monomers were potentiostatically electropolymerized upon confinement in 1D channels of a surface-mounted metal-organic framework Cu(BDC) (SURMOF-2). A layer-by-layer deposition method allowed for SURMOF depostition on substrates with prepatterned electrodes, making it possible to characterize electrical conductivity in situ, i.e., without having to delaminate the conductive polymer thin film. Successful polymerization was evidenced by mass spectroscopy, and the electrical measurements demonstrated an increase of the electrical conductivity of the MOF material by 8 orders of magnitude. Extensive DFT calculations revealed that the final conductivity is limited by electron hopping between the conductive oligomers.