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CeO2-supported noble metal clusters are attractive catalytic materials for several applications. However, their atomic dispersion under oxidizing reaction conditions often leads to catalyst deactivation. In this study, the noble metal cluster formation threshold is rationally adjusted by using a mixed CeO2-Al2O3 support. The preferential location of Pd on CeO2 islands leads to a high local surface noble metal concentration and promotes the in situ formation of small Pd clusters at a rather low noble metal loading (0.5â wt %), which are shown to be the active species for CO conversion at low temperatures. As elucidated by complementary in situ/operando techniques, the spatial separation of CeO2 islands on Al2O3 confines the mobility of Pd, preventing the full redispersion or the formation of larger noble metal particles and maintaining a high CO oxidation activity at low temperatures. In a broader perspective, this approach to more efficiently use the noble metal can be transferred to further systems and reactions in heterogeneous catalysis.
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The surface structure and chemical properties of Y-stabilized zirconia (YSZ) have been subjects of intense debate over the past three decades. However, a thorough understanding of chemical processes occurring at YSZ powders faces significant challenges due to the absence of reliable reference data acquired for well-controlled model systems. Here, we present results from polarization-resolved infrared reflection absorption spectroscopy (IRRAS) obtained for differently oriented, Y-doped ZrO2 single-crystal surfaces after exposure to CO and D2O. The IRRAS data reveal that the polar YSZ(100) surface undergoes reconstruction, characterized by an unusual, red-shifted CO band at 2132â cm-1. Density functional theory calculations allowed to relate this unexpected observation to under-coordinated Zr4+ cations in the vicinity of doping-induced O vacancies. This reconstruction leads to a strongly increased chemical reactivity and water spontaneously dissociates on YSZ(100). The latter, which is an important requirement for catalysing the water-gas-shift (WGS) reaction, is absent for YSZ(111), where only associative adsorption was observed. Together with a novel analysis Scheme these reference data allowed for an operando characterisation of YSZ powders using DRIFTS (diffuse reflectance infrared Fourier transform spectroscopy). These findings facilitate rational design and tuning of YSZ-based powder materials for catalytic applications, in particular CO oxidation and the WGS reaction.
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Thin films of crystalline solids with substantial free volume built from organic chromophores and metal secondary building units (SBUs) are promising for engineering new optoelectronic properties through control of interchromophore coupling. Zn-based SBUs are especially relevant in this case because they avoid quenching the chromophore's luminescence. We find that layer-by-layer spin-coating using Zn acetate dihydrate and benzene-1,4-dicarboxylic acid (H2BDC) and biphenyl-4,4'-dicarboxylic acid (H2BPDC) linkers readily produces crystalline thin films. However, analysis of the grazing-incidence wide-angle X-ray scattering (GIWAXS) data reveals the structures of these films vary significantly with the linker, and with the metal-to-linker molar ratio used for fabrication. Under equimolar conditions, H2BPDC creates a type of structure like that proposed for SURMOF-2, whereas H2BDC generates a different metal-hydroxide-organic framework. Large excess of Zn2+ ions causes the growth of layered zinc hydroxides, irrespective of the linker used. Density functional theory (DFT) calculations provide structural models with minimum total energy that are consistent with the experimentally observed diffractograms. In the broader sense, this work illustrates the importance in this field of careful structure determination, e. g., by utilizing GIWAXS and DFT simulations to determine the structure of the obtained crystalline metal-organic thin films, such that properties can be rationally engineered and explained.
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In the last few years, infrared reflection-absorption spectroscopy (IRRAS) has become a standard technique to study vibrational excitations of molecules. These investigations are strongly motivated by potential applications in monitoring chemical processes. For a better understanding of the adsorption mechanism of molecules on dielectrics, the polarization-dependence of an interaction of infrared light with adsorbates on dielectric surfaces is commonly used. Thus, the peak positions in absorption spectra could be different for s- and p-polarized light. This shift between the peak positions depends on both the molecule itself and the dielectric substrate. While the origin of this shift is well understood for infinite two-dimensional adsorbate layers, finite-size samples, which consist of 2D islands of a small number of molecules, have never been considered. Here, we present a study on polarization-dependent finite-size effects in the optical response of such islands on dielectric substrates. The study uses a multi-scale modeling approach that connects quantum chemistry calculations with Maxwell scattering simulations. We distinguish the optical response of a single molecule, a finite number of molecules, and a two-dimensional adsorbate layer. We analyze CO and CO2 molecules deposited on CeO2 and Al2O3 substrates. The evolution of the shift between the polarization-dependent absorbance peaks is first studied for a single molecule, which does not exhibit any shifting at all, and for finite molecular islands, where it increases with increasing island size, as well as for an infinite two-dimensional adsorbate layer. In the latter case, the agreement between the obtained results and the experimental IRRAS data and more traditional three/four-layer model theoretical studies supports the predictive power of the multi-scale approach.
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Metal-organic frameworks (MOFs), with their well-defined and highly flexible nanoporous architectures, provide a material platform ideal for fabricating sensors. We demonstrate that the efficacy and specificity of detecting and differentiating volatile organic compounds (VOCs) can be significantly enhanced using a range of slightly varied MOFs. These variations are obtained via postsynthetic modification (PSM) of a primary framework. We alter the original MOF's guest adsorption affinities by incorporating functional groups into the MOF linkers, which yields subtle changes in responses. These responses are subsequently evaluated by using machine learning (ML) techniques. Under severe conditions, such as high humidity and acidic environments, sensor stability and lifespan are of utmost importance. The UiO-66-X MOFs demonstrate the necessary durability in acidic, neutral, and basic environments with pH values ranging from 2 to 11, thus surpassing most other similar materials. The UiO-66-NH2 thin films were deposited on quartz-crystal microbalance (QCM) sensors in a high-temperature QCM liquid cell using a layer-by-layer pump method. Three different, highly stable surface-anchored MOFs (SURMOFs) of UiO-66-X obtained via the PSM approach (X: NH2, Cl, and N3) were employed to fabricate arrays suitable for electronic nose applications. These fabricated sensors were tested for their capability to distinguish between eight VOCs. Data from the sensor array were processed using three distinct ML techniques: linear discriminant (LDA), nearest neighbor (k-NN), and neural network analysis methods. The discrimination accuracies achieved were nearly 100% at high concentrations and over 95% at lower concentrations (50-100 ppm).
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Estructuras Metalorgánicas , Ácidos Ftálicos , Compuestos Orgánicos Volátiles , AdsorciónRESUMEN
Electron-phonon interactions, crucial in condensed matter, are rarely seen in Metal-Organic Frameworks (MOFs). Detecting these interactions typically involves analyzing luminescence in lanthanide- or actinide-based compounds. Prior studies on Ln- and Ac-based MOFs at high temperatures revealed additional peaks, but these were too faint for thorough analysis. In our research, we fabricated a high-quality, crystalline uranium-based MOF (KIT-U-1) thin film using a layer-by-layer method. Under UV light, this film showed two distinct "hot bands," indicating a strong electron-phonon interaction. At 77â K, these bands were absent, but at 300â K, a new emission band appeared with half the intensity of the main luminescence. Surprisingly, a second hot band emerged above 320â K, deviating from previous findings in rare-earth compounds. We conducted a detailed ab-initio analysis employing time-dependent density functional theory to understand this unusual behaviour and to identify the lattice vibration responsible for the strong electron-phonon coupling. The KIT-U-1 film's hot-band emission was then utilized to create a highly sensitive, single-compound optical thermometer. This underscores the potential of high-quality MOF thin films in exploiting the unique luminescence of lanthanides and actinides for advanced applications.
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Metal-organic frameworks (MOFs), are porous crystalline structures comprising of metal ions or clusters intricately linked with organic entities, displaying topological diversity and effortless chemical flexibility. These characteristics render them apt for multifarious applications such as adsorption, separation, sensing, and catalysis. Predominantly, the distinctive properties and prospective utility of MOFs are discerned post-manufacture or extrapolation from theoretically conceived models. For empirical researchers unfamiliar with hypothetical structure development, the meticulous crystal engineering of a high-performance MOF for a targeted application via a bottom-up approach resembles a gamble. For example, the precise pore limiting diameter (PLD), which determines the guest accessibility of any MOF cannot be easily inferred with mere knowledge of the metal ion and organic ligand. This limitation in bottom-up conceptual understanding of specific properties of the resultant MOF may contribute to the cautious industrial-scale adoption of MOFs.Consequently, in this study, we take a step towards circumventing this limitation by designing a new tool that predicts the guest accessibility-a MOF key performance indicator-of any given MOF from information on only the organic linkers and the metal ions. This new tool relies on clustering different MOFs in a galaxy-like social network, MOFGalaxyNet, combined with a Graphical Convolutional Network (GCN) to predict the guest accessibility of any new entry in the social network. The proposed network and GCN results provide a robust approach for screening MOFs for various host-guest interaction studies.
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As the world population continues to grow, there is also a rising concern regarding water pollution since this condition could negatively impact the supply of clean water. One of the most recent concerns is related to the pollution that comes from various pharmaceuticals, in particular non-steroidal anti-inflammatory drugs (NSAIDs) since they have been industrially produced at large scale and can be easily purchased as an over-the-counter medicine. Diclofenac is one of the most popular NSAIDs because of its high-effectiveness, which leads to its excessive consumption. Consequently, its presence in water bodies is also continuously increasing. An adsorption process could then be employed as a highly effective method to address this issue. In comparison to other conventional adsorbents such as activated carbon, the use of metal-organic frameworks (MOFs) as an alternative adsorbent is very attractive since it can offer various advantages such as tailorability and high adsorption capacity. In this study, the performance of three water-stable, free-base porphyrin MOFs assembled using zirconia-based nodes, namely MOF-525, MOF-545, and NU-902, for diclofenac adsorption was thoroughly investigated. Interestingly, although all three free-base porphyrin MOFs are assembled using the same building block and have a similar specific surface area (based on the experimental argon physisorption and calculation based on non-localized density functional theory), their diclofenac adsorption capacity is substantially different from one another. It is found that the highest diclofenac adsorption capacity is shown by MOF-525, which has maximum capacity around 792 mg g-1. This is then followed by MOF-545 and NU-902 that have adsorption capacities around 591 and 486 mg g-1, respectively. Some possible adsorption mechanisms are then thoroughly discussed that might contribute to this phenomenon. Lastly, their performance is also compared with other MOFs that are also studied for this purpose to show their performance superiority not only in terms of adsorption capacity but also their affinity towards the diclofenac molecule, which might be useful as an adsorption performance indicator in the real condition where the contaminant concentration is considerably low.
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The facet-dependent adsorption of CO on oxidized and reduced CeO2 single crystal surfaces is reviewed, with emphasis on the effect of CO coverage and the ability of state-of-the-art quantum-mechanical methods to provide reliable energies and an accurate description of the IR vibrational frequency of CO. Comparison with detailed, high-resolution experimental infrared reflection absorption spectroscopy data obtained for single crystal samples allows the assignment of the different CO vibrational bands observed on all three low-index ceria surfaces. Good agreement is achieved with the hybrid density functional theory approach with the HSE06 functional and with saturation coverage. It is shown that CO is very sensitive to the structure of cerium oxide surfaces and to the presence of oxygen vacancies. The combined theoretical-experimental approach offers new opportunities for a better characterization of ceria nanoparticles and for unraveling changes occurring during reactions involving CO at higher pressures.
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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.
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Industrial biocatalysis plays an important role in the development of a sustainable economy, as enzymes can be used to synthesize an enormous range of complex molecules under environmentally friendly conditions. To further develop the field, intensive research is being conducted on process technologies for continuous flow biocatalysis in order to immobilize large quantities of enzyme biocatalysts in microstructured flow reactors under conditions that are as gentle as possible in order to realize efficient material conversions. Here, monodisperse foams consisting almost entirely of enzymes covalently linked via SpyCatcher/SpyTag conjugation are reported. The biocatalytic foams are readily available from recombinant enzymes via microfluidic air-in-water droplet formation, can be directly integrated into microreactors, and can be used for biocatalytic conversions after drying. Reactors prepared by this method show surprisingly high stability and biocatalytic activity. The physicochemical characterization of the new materials is described and exemplary applications in biocatalysis are shown using two-enzyme cascades for the stereoselective synthesis of chiral alcohols and the rare sugar tagatose.
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Alcoholes , Enzimas Inmovilizadas , Biocatálisis , Enzimas Inmovilizadas/metabolismo , EnzimasRESUMEN
The potential of chiral metal-organic frameworks (MOFs) for circularly polarized (CP) optics has been largely unexplored. Herein, we have successfully deposited monolithic and highly oriented chiral MOF thin films prepared by a layer-by-layer method (referred to as surface-coordinated MOF thin films, SURMOF) to fabricate CP photodetection devices and distinguish enantiomers. The helicity-sensitive absorption induced by a pair of enantiopure oriented SURMOF was found to be excellent, with an anisotropy factor reaching 0.41. Moreover, the chiral SURMOFs exhibited a pronounced difference in the uptake of the l- and d-tryptophan enantiomers. To demonstrate the potential of these novel MOF thin films for chirality analysis, we fabricated a portable sensor device that allows for chiral recognition by monitoring the photocurrent signals. Our findings not only introduce a new concept of using chiral building blocks for realizing direct CP photodetectors but also provide a blueprint for novel devices in chiral optics.
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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.
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Easy-to-integrate, remote read-out thermometers with fast response are of huge interest in numerous application fields. In the context of optical read-out devices, sensors based on the emission of lanthanides (Eu(III), Tb(III)) are particularly promising. Here, by using a layer-by-layer (LbL) approach in the liquid-phase epitaxy process, a series of continuous, low-thickness lanthanide-MIL-103 SURMOFs were fabricated to yield highly sensitive thermometers with optical readout. These Ln-SURMOFs exhibit remarkable temperature-sensing photoluminescence behavior, which can be read out using the naked eye. High transmittance is realized as well by precisely controlling the film thickness and the quality of these Ln-SURMOF thermometers. Moreover, we demonstrate that the thermal sensitivity can be improved in the temperature regime above 120 K, by controlling the energy transfer between Tb(III) and Eu(III). This performance is achieved by employing a sophisticated supramolecular architecture, namely MOF-on-MOF heteroepitaxy.
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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.
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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.
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The interaction of CaO and Ca(OH)2 with solvated or gaseous SO2 plays a crucial role in the corrosion of urban infrastructure by acid rain or in the removal of SO2 from flue gas. We carried out a combined spectroscopic and theoretical investigation on the interaction of SO2 with a CaO(001) single crystal. First, the surface chemistry of SO2 was investigated at different temperatures using polarization-resolved IR reflection absorption spectroscopy. Three species were identified, and an in-depth density functional theory study was carried out, which allowed deriving a consistent picture. Unexpectedly, low temperature exposure to SO2 solely yields a physisorbed species. Only above 100â K, the transformation of this weakly bound adsorbate first to a chemisorbed sulfite and then to a sulfate occurs, effectively passivatating the surface. Our results provide the basis for more efficient strategies in corrosion protection of urban infrastructure and in lime-based desulfurization of flue gas.
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In this report, we describe a modular synthesis approach towards a new series of non-centrosymmetric, dipolar 4,4'-bipyridines bearing 2,6- and 3,5-functionalized pyridyl moieties at the peripheries. Central to our strategy is the selective substitution on only one pyridyl motif that could contain electron-donating (-CH3 ) or electron-withdrawing (-F, -Cl, -CF3 ) groups which causes electronic/steric effects on one nitrogen atom in 4,4'-bipyridines. This synthetic protocol was further applied to prepare azo-functionalized (-N=N-) asymmetric bipyridines and non-centrosymmetric 4,4'-bipyridine N-oxide scaffolds, which overcome the synthetic hurdles oxidizing 4,4'-bipyridines to N-monoxides selectively at only one pyridine. Compared to the conventional symmetrical bipyridines, the dipolar non-centrosymmetric molecular tectons pave the way for the realization of non-centrosymmetric supramolecular assemblies because of the difference in the binding energy of the pyridyl nitrogen atoms.