Search

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.

The unique properties of 2D-materials like graphene are exploited in various electronic devices. In sensor applications, graphene shows a very high sensitivity, but only a low specificity. This shortcoming can be mastered by using heterostructures, where graphene is combined with materials exhibiting high analyte selectivities. Herein, this study demonstrates the precise deposition of nanoporous metal-organic frameworks (MOFs) on graphene, yielding bilayers with excellent specificity while the sensitivity remains large. The key for the successful layer-by-layer deposition of the MOF films (SURMOFs) is the use of planar polyaromatic anchors. Then, the MOF pores are loaded with ionic liquid (IL). For functioning sensor devices, the IL@MOF films are grown on graphene field-effect transistors (GFETs). Adding a top-gate electrode yields an ion-gated GFET. Analysis of the transistor characteristics reveals a clear Dirac point at low gate voltages, good on-off ratios, and decent charge mobilities and densities in the graphene channel. The GFET-sensor reveals a strong and selective response. Compared to other ion-gated-FET devices, the IL@MOF material is relatively hard, allowing the manufacturing of ultrathin devices. The new MOF-anchoring strategy offers a novel approach generally applicable for the functionalization of 2D-materials, where MOF/2D-material hetero-bilayers carry a huge potential for a wide variety of applications.

The conduction of protons and other ions in nanoporous materials, such as metal-organic frameworks (MOFs), is intensively explored with the aim of enhancing the performance of energy-related electrochemical systems. The ionic conductivity, as a key property of the material, is typically determined by using electrochemical impedance spectroscopy (EIS) in connection with a suitable equivalent circuit. Often, equivalent circuits are used where the physical meaning of each component is debatable. Here, we present an equivalent circuit for the ionic conduction of electrolytes in nanoporous, nonconducting materials between inert and impermeable electrodes without faradaic electrode reactions. We show the equivalent circuit perfectly describes the impedance spectra measured for the ion conduction in MOFs in the form of powders pressed into pellets as well as for MOF thin films. This is demonstrated for the ionic conduction of an aprotic ionic liquid, and of various protic solvents in different MOF structures. Due to the clear physical meaning of each element of the equivalent circuit, further insights into the electrical double layer forming at the MOF-electrode interface can be obtained. As a result, EIS combined with the appropriate reference circuit allows us to make statements of the quality of the MOF-substrate interface of different MOF-film samples.

Structurally well‐defined, crystalline organic/organic heterojunctions between C60‐ and anthracene‐based semiconductors are realized via layer‐by‐layer deposition of metal‐organic framework, MOF, thin films. As demonstrated by X‐ray diffraction, perfect epitaxy is achieved by adjusting the lattice constants of the two different MOFs. Deposition of top electrodes allows to fabricate p–n as well as n–p devices. Measurements of the electrical properties reveal the presence of high‐performance diodes, with a current on/off ratio of up to 6 orders of magnitude and an ideality factor close to unity. The crystalline nature of the abrupt organic/organic heterojunction provides the basis for a rational, simulation‐based optimization and tailoring of such organic semiconductor interfaces., Crystalline abrupt organic/organic heterojunctions are presented. This is realized by incorporating semiconducting molecules, here anthracene and C60, in metal‐organic framework thin films fabricated in a layer‐by‐layer fashion forming bilayer films. The p–n‐junctions show strong diode performance with a current rectification of up to six orders of magnitude.

The mass transfer of the guest molecules in nanoporous host materials, in particular in metal-organic frameworks (MOFs), is among the crucial features of their applications. By using thin surface-mounted MOF films in combination with a quartz crystal microbalance (QCM), the diffusion of ferrocene vapor and of ethanolic and hexanic ferrocene solution in HKUST-1 was investigated. For the first time, liquid- and gas-phase diffusion in MOFs was compared directly in the identical sample. The diffusion coefficients are in the same order of magnitude (~10$^{-16}$ m$^{2}$·s$^{-1}$), whereas the diffusion coefficient of ferrocene in the empty framework is roughly 3-times smaller than in the MOF which is filled with ethanol or n-hexane.

Metal-organic frameworks offer tremendous potential for efficient separation of molecular mixtures. Different pore sizes and suitable functionalizations of the framework allow for an adjustment of the static selectivity. Here we report membranes which offer dynamic control of the selectivity by remote signals, thus enabling a continuous adjustment of the permeate flux. This is realized by assembling linkers containing photoresponsive azobenzene-side-groups into monolithic, crystalline membranes of metal-organic frameworks. The azobenzene moieties can be switched from the trans to the cis configuration and vice versa by irradiation with ultraviolet or visible light, resulting in a substantial modification of the membrane permeability and separation factor. The precise control of the cis:trans azobenzene ratio, for example, by controlled irradiation times or by simultaneous irradiation with ultraviolet and visible light, enables the continuous tuning of the separation. For hydrogen:carbon-dioxide, the separation factor of this smart membrane can be steplessly adjusted between 3 and 8., The tunable pore size and functionalization of metal-organic frameworks offers great potential for efficient and selective separation of molecular mixtures. Here, the authors report a metal-organic membrane containing photoresponsive linkers which offers a dynamic control of selectivity by remote signals

The use of optical techniques, such as interference microscopy and IR micro-imaging, has enabled the direct observation of transient concentration profiles. In a one-dimensional crystal, surface permeabilities on opposing crystal faces are usually equal, so that mass transfer occurs symmetrically and the fluxes through both crystal faces are identical. If the surface permeabilities on opposing crystal faces are different from each other, mass transfer is not symmetrical anymore. We are going to show that the fraction of molecular uptake (or release) through a given host face is inversely proportional to the time constant of uptake/release via this crystal face. This finding permits a straightforward estimate of the influence of asymmetry on overall uptake.

Boltzmann’s integration method may prove to be a very powerful tool to study the transport diffusion of guest molecules in nanoporous host systems. In many cases, however, the prerequisites for applying this method are not completely fulfilled. In the following, the consequences of these deviations on the accuracy of the obtained results are discussed. It is found that the results of Boltzmann’s integration method can be corrected by different considerations. The discussion is focussed on the concentration profiles observed during the adsorption and desorption of methanol in ferrierite-type crystals as observable by interference microscopy.

The intracrystalline concentration profiles evolving during molecular uptake and release by nanoporous materials as accessible by interference microscopy contain a lot of hidden information. For concentration-independent transport parameter, the influence of surface resistances to overall mass transfer can be calculated by correlating the actual surface concentration with the overall uptake. By using a numerical solution of Fick’s 2nd law and considering a large variety of concentration dependencies of the transport diffusivity and the surface permeability, we show that the factor by which the transport process is retarded by the surface resistance may reasonably well be estimated by the type of correlation between the actual boundary concentration and the total uptake at a given time. In this way, a novel technique of uptake analysis which may analytically be shown to hold for constant diffusivities and surface permeabilities, is shown to be quite generally applicable.

Photoschalter sind Moleküle, die eine reversible lichtgesteuerte Umwandlung zwischen zwei Zuständen mit unterschiedlichen Eigenschaften durchlaufen. In den letzten zehn Jahren hat der Einbau dieser photochromen Moleküle in intelligente, auf Stimuli ansprechende Materialien zunehmende Aufmerksamkeit erregt, da sie die einzigartige Fähigkeit bieten, makroskopische Eigenschaften mit einem externen optischen Stimulus reversibel zu verstärken und zu verändern. Die begrenzte Leistung von Photoschaltern in festen Medien bleibt eine Herausforderung. In diesem Zusammenhang werden in dieser Arbeit zwei wichtige Aspekte näher untersucht. Erstens der Prozess der Entwicklung neuer Photoschalter mit maßgeschneiderten Eigenschaften und zweitens die Implementierung von Photoschaltern in feste Materialien und die damit verbundenen Herausforderungen. Im ersten Teil dieser Arbeit wurde Dynamisch-kovalente Chemie (DCC) verwendet, um die Entdeckung und Entwicklung einer neuartigen Klasse von Photoschaltern mit drei Zuständen zu beschleunigen. Die dynamische Natur der zentralen Doppelbindung von α-Cyanodiarylethenen wurde genutzt, um ein thermodynamisches Gleichgewicht mit anderen Arylacetonitrilen herzustellen. Die entwickelte Methode kombiniert eine schnelle Diversifizierung mit einer Rasterung auf spezifische Eigenschaften, die durch einen externen Stimulus aufgedeckt werden, und ermöglicht die effiziente Untersuchung der Beziehung zwischen Struktur und den zugehörigen Eigenschaften. Im zweiten Teil der Arbeit wird die Entwicklung und die Synthese eines Zweikomponenten-Kern-Schale-MOFs mit einem internen nicht-funktionalisierten Kompartiment, das von einer dünnen photoschaltbaren Außenschale bedeckt ist, vorgestellt. Diese Strategie ermöglicht ein effizientes Schalten des Chromophors und die resultierende dünne „intelligente“ Schale fungiert als modulare kinetische Barriere für die molekulare Gastdiffusion in das Material, die durch Licht gesteuert werden kann., Photoswitches are molecules that undergo a reversible light-triggered conversion between two states with different properties. In the past decade, the incorporation of these photochromic molecules in smart stimuli-responsive materials has gained increased attention as it offers the unique ability to reversibly amplify and change macroscopic properties with an external optical stimulus. The limited performance of photoswitches in solid mediums remains a challenge. In this context two important aspects are studied in more detail in this thesis. First, the process of developing new photoswitches with tailored properties and second, the implementation of photoswitches in solid materials and the challenges associated with it. In the first part of this thesis dynamic covalent chemistry (DCC) was used to accelerate the discovery and development of a novel three-state photoswitch class. The dynamic nature of the central double bond of α-cyanodiarylethenes was exploited to establish a thermodynamic equilibrium with other arylacetonitriles. The developed DCC tool combines fast and efficient diversification with screening for specific photochemical properties revealed by an external stimulus, enabling the rapid study of the relationship between structure and the associated properties. The second part of this thesis summarizes the design and synthesis of a two-component core-shell MOF with an internal non-functionalized compartment covered by a thin photoswitchable outer shell. This strategy allows efficient switching of the chromophore and the resulting thin “smart” shell acts as a modular kinetic barrier for molecular guest diffusion into the material that can be controlled by light.