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The valorization of carbon dioxide as a C1 building block in C-C bond forming reactions is a critical link on the road to carbon-circular chemistry. Activation of this inert molecule through reduction with H2 to carbon monoxide in the reverse water-gas shift (RWGS) reaction can be followed by a wide spectrum of consecutive carbonylation reactions, but the RWGS is severely equilibrium limited at the moderate temperatures of carbonylations. Here we successfully reconcile both reactions in one pot, while avoiding incompatibilities through a zeolite-based compartmentalized approach. More specifically, Pt encapsulated in a small-pore LTA zeolite selectively generates carbon monoxide in mild reaction conditions; an ensuing one-pot carbonylation reaction allows to shift the equilibrium through continuous consumption of CO. Moreover, the zeolite encapsulation avoids undesired reactions like hydrogenation of the olefin reactant through a molecular sieving effect. This strategy was first studied in-depth for Rh-catalyzed olefin hydroformylation with CO2/H2, affording aldehydes in good yields with high regioselectivities. The methodology was then extended to a variety of carbonylations using CO2 for the synthesis of bulk and fine chemicals., (© 2024 Wiley‐VCH GmbH.)

In living tissues, cells express their functions following complex signals from their surrounding microenvironment. Capturing both hierarchical architectures at the micro- and macroscale, and anisotropic cell patterning remains a major challenge in bioprinting, and a bottleneck toward creating physiologically-relevant models. Addressing this limitation, a novel technique is introduced, termed Embedded Extrusion-Volumetric Printing (EmVP), converging extrusion-bioprinting and layer-less, ultra-fast volumetric bioprinting, allowing spatially pattern multiple inks/cell types. Light-responsive microgels are developed for the first time as bioresins (µResins) for light-based volumetric bioprinting, providing a microporous environment permissive for cell homing and self-organization. Tuning the mechanical and optical properties of gelatin-based microparticles enables their use as support bath for suspended extrusion printing, in which features containing high cell densities can be easily introduced. µResins can be sculpted within seconds with tomographic light projections into centimeter-scale, granular hydrogel-based, convoluted constructs. Interstitial microvoids enhanced differentiation of multiple stem/progenitor cells (vascular, mesenchymal, neural), otherwise not possible with conventional bulk hydrogels. As proof-of-concept, EmVP is applied to create complex synthetic biology-inspired intercellular communication models, where adipocyte differentiation is regulated by optogenetic-engineered pancreatic cells. Overall, EmVP offers new avenues for producing regenerative grafts with biological functionality, and for developing engineered living systems and (metabolic) disease models., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Understanding the impact of shaping processes on solid adsorbents is critical for the implementation of MOFs in industrial separation processes or as catalytic materials. Production of MOF-containing shaped particles is typically associated with loss of porosity and modification of acid sites, two phenomena that affect their performance. Herein, we report a detailed study on how extrusion affects the crystallinity, porosity, and acidity of the aluminium fumarate MOF with clays or SiO 2 gel binders. Thorough characterization showed that the clay binders confer the extrudates a good mechanical robustness at the expense of porosity, while silica gel shows an opposite trend. The CO 2 selectivity towards CH 4 , of interest for natural gas separation processes, is maintained upon the extrusion process. Moreover, probe FTIR spectroscopy revealed no major changes in the types of acid sites. This study highlights that these abundant and inexpensive clay materials may be used for scaling MOFs as active adsorbents., (© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Thin films of crystalline and porous metal-organic frameworks (MOFs) have great potential in membranes, sensors, and microelectronic chips. While the morphology and crystallinity of MOF films can be evaluated using widely available techniques, characterizing their pore size, pore volume, and specific surface area is challenging due to the low amount of material and substrate effects. Positron annihilation lifetime spectroscopy (PALS) is introduced as a powerful method to obtain pore size information and depth profiling in MOF films. The complementarity of this approach to established physisorption-based methods such as quartz crystal microbalance (QCM) gravimetry, ellipsometric porosimetry (EP), and Kr physisorption (KrP) is illustrated. This comprehensive discussion on MOF thin film porosimetry is supported by experimental data for thin films of ZIF-8., (© 2021 Wiley-VCH GmbH.)

Energy-efficient indoors temperature and humidity control can be realised by using the reversible adsorption and desorption of water in porous materials. Stable microporous aluminium-based metal-organic frameworks (MOFs) present promising water sorption properties for this goal. The development of synthesis routes that make use of available and affordable building blocks and avoid the use of organic solvents is crucial to advance this field. In this work, two scalable synthesis routes under mild reaction conditions were developed for aluminium-based MOFs: (1) in aqueous solutions using a continuous-flow reactor and (2) through the vapour-assisted conversion of solid precursors. Fumaric acid, its methylated analogue mesaconic acid, as well as mixtures of the two were used as linkers to obtain polymorph materials with tuneable water sorption properties. The synthesis conditions determine the crystal structure and either the MIL-53 or MIL-68 type structure with square-grid or kagome-grid topology, respectively, is formed. Fine-tuning resulted in new MOF materials thus far inaccessible through conventional synthesis routes. Furthermore, by varying the linker ratio, the water sorption properties can be continuously adjusted while retaining the sigmoidal isotherm shape advantageous for heat transformation and room climatisation applications., (© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Split-phase alcoholysis of flexible polyurethane (PU) foam yields an apolar phase containing the recycled polyether polyol, and a lower, polar phase of the alcoholyzing agent and aromatic compounds. However, multiple purification steps are required to render the polyether polyol suitable for synthesis of new flexible PU foams; the unfavorable mass balance limits industrial applications. In this work, 2-pyrrolidone was identified as a performant additive for accelerating the dissolution and depolymerization process. By applying a lactam to PU foam in a weight ratio of 0.1:1, the glycol to PU foam weight ratio can be decreased from 1.5:1 to only 0.5:1, without loss of purity or yield of the recycled polyether polyol. Diglycerol was discovered as a novel, promising alcoholyzing agent; it allows the recycling of the polyether polyol in high purity (97 %) and excellent yields (98 %), and after a single washing with diglycerol, a sufficiently low hydroxyl value (61 mg KOH  g -1 ) is reached. The recycled polyether polyol can replace the virgin polyether polyol (48 mg KOH  g -1 ) for up to 50 % in the synthesis of new flexible PU foams with effects on the foam quality that stay within the limits of generally accepted specifications. A first step towards the valorization of the lower phase was also taken by applying hydrolysis of the newly formed carbamates to toluenediamines, which are readily reintegrated in new PU foams., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Herein, AlK α X-rays are used to drive the growth of luminescent silver clusters in zeolites. The growth of the silver species is tracked using Auger spectroscopy and fluorescence microscopy, by monitoring the evolution from their ions to luminescent clusters and then metallic, dark nanoparticles. It is shown that the growth rate in different zeolites is determined by the mobility of the silver ions in the framework and that the growth dynamics in calcined samples obeys the Hill-Langmuir equation for noncooperative binding. Comparison of the optical properties of X-ray-grown silver clusters with silver clusters formed by standard heat treatment indicates that the latter have a higher specificity toward the formation of luminescent clusters of a specific (small) nuclearity, whereas the former produce a wide distribution of cluster species as well as larger nanoparticles., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The capping formate anions of the metal-organic framework (MOF) zirconium benzene-1,3,5-tricarboxylate (MOF-808) were removed by a solvent exchange procedure, resulting in a formate-free MOF-808 sample containing "geminal" defects consisting of six coordinatively unsaturated sites (CUSs) on each of the Zr 6 nodes. Adsorption experiments with this material showed that the uptake of 4-methylguaiacol from a bio-oil mixture was proportional to the number of defects and amounted to one mole adsorbed per mole of zirconium. The selective uptake behavior of MOF-808 towards phenolic compounds was further evident from competitive adsorption experiments between furfuryl alcohol and 4-methylguaiacol as well as from the excellent (20 wt % for phenolic compounds and <7 wt % for other compounds) uptake performance for real bio-oil mixtures containing a large concentration and diversity of molecules., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Citric acid (CA) is an important organic acid that is produced on a large scale by fermentation. Current methods to recover CA from the fermentation broth require large amounts of chemicals and produce considerable amounts of waste, while not all CA can be recovered. The use of adsorbents can increase the degree of product recovery and reduce chemical consumption and waste generation. In this work, poly(4-vinylpyridine) (PVP) is evaluated as an adsorbent for CA recovery. It has a high adsorption capacity (>30 wt %) at low pH and a high selectivity for CA at moderate pH in the presence of sulfate anions, two conditions that are frequently encountered during CA recovery. PVP could be efficiently regenerated after adsorption using simple alcohols like methanol and ethanol. Considering selectivity and regeneration, PVP distinctly outperforms more common adsorbents for organic acids, including commercial strongly and weakly basic anion exchangers. The desirable adsorptive features of PVP for CA can be attributed to the low basicity of the pyridine group., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

One of the major requirements in solid acid and base catalyzed reactions is that the reactants, intermediates or activated complexes cooperate with several functions of catalyst support. In this work the remarkable bifunctional behavior of the defective UiO-66(Zr) metal organic framework is shown for acid-base pair catalysis. The active site relies on the presence of coordinatively unsaturated zirconium sites, which may be tuned by removing framework linkers and by removal of water from the inorganic bricks using a dehydration treatment. To elucidate the amphoteric nature of defective UiO-66, the Oppenauer oxidation of primary alcohols has been theoretically investigated using density functional theory (DFT) and the periodic approach. The presence of acid and basic centers within molecular distances is shown to be crucial for determining the catalytic activity of the material. Hydrated and dehydrated bricks have a distinct influence on the acidity and basicity of the active sites. In any case both functions need to cooperate in a concerted way to enable the chemical transformation. Experimental results on UiO-66 materials of different defectivity support the theoretical observations made in this work.

Biomass-derived lactic acid (LA) is an important platform chemical towards the sustainable production of numerous materials. However, the fermentation process currently in use is limited by the difficult recovery of the LA product from the fermentation broth and results in the generation of stoichiometric amounts of gypsum waste. Herein, we show that metal-organic frameworks (MOFs) of the UiO-66(Zr) type are effective adsorbents for the separation of LA from aqueous (buffer) solutions. These frameworks based on zirconium clusters and terephthalic acid derivatives display a tremendous uptake (up to 42 wt %) and a high affinity for LA. The latter can further be tuned by changing the hydrogen-bonding properties of the functional groups present on the organic ligand. A Rietveld refinement disclosed the specific interaction of LA with the clusters of UiO-66(Zr) and a preferential adsorption on open zirconium sites. Taking advantage of the catalytic activity of UiO-66(Zr), desorption of LA was performed in alcohols to recover up to 73 % as ester. Applied to the recovery of LA, adsorption and reactive desorption offer a direct and gypsum-free strategy as an alternative for the current multi-step process., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Materials processing, and thin-film deposition in particular, is decisive in the implementation of functional materials in industry and real-world applications. Vapor processing of materials plays a central role in manufacturing, especially in electronics. Metal-organic frameworks (MOFs) are a class of nanoporous crystalline materials on the brink of breakthrough in many application areas. Vapor deposition of MOF thin films will facilitate their implementation in micro- and nanofabrication research and industries. In addition, vapor-solid modification can be used for postsynthetic tailoring of MOF properties. In this context, we review the recent progress in vapor processing of MOFs, summarize the underpinning chemistry and principles, and highlight promising directions for future research., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The isoreticular analogue of the metal-organic framework UiO-66(Zr), synthesized with the flexible trans-1,4-cyclohexanedicarboxylic acid as linker, shows a peculiar breathing behavior by reversibly losing long-range crystalline order upon evacuation. The underlying flexibility is attributed to a concerted conformational contraction of up to two thirds of the linkers, which breaks the local lattice symmetry. X-ray scattering data are described well by a nanodomain model in which differently oriented tetragonal-type distortions propagate over about 7-10 unit cells., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The synthesis of titanium-carboxylate metal-organic frameworks (MOFs) is hampered by the high reactivity of the commonly employed alkoxide precursors. Herein, we present an innovative approach to titanium-based MOFs by the use of titanocene dichloride to synthesize COK-69, the first breathing Ti MOF, which is built up from trans-1,4-cyclohexanedicarboxylate linkers and an unprecedented [Ti(IV)3(μ3-O)(O)2(COO)6] cluster. The photoactive properties of COK-69 were investigated in depth by proton-coupled electron-transfer experiments, which revealed that up to one Ti(IV) center per cluster can be photoreduced to Ti(III) while preserving the structural integrity of the framework. The electronic structure of COK-69 was determined by molecular modeling, and a band gap of 3.77 eV was found., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The isolation and separation of phenolic compounds from aqueous backgrounds is challenging and will gain in importance as we become more dependent on phenolics from lignocellulose-derived bio-oil to meet our needs for aromatic compounds. Herein, we show that highly stable and hydrophobic Zr metal-organic frameworks of the MIL-140 type are effective adsorbent materials for the separation of different phenolics and far outperform other classes of porous solids (silica, zeolites, carbons). The mechanism of the hydroquinone-catechol separation on MIL-140C was studied in detail by combining experimental results with computational techniques. Although the differences in adsorption enthalpy between catechol and hydroquinone are negligible, the selective uptake of catechol in MIL-140C is explained by its dense π-π stacking in the pores. The interplay of enthalpic and entropic effects allowed separation of a complex, five-compound phenol mixture through breakthrough over a MIL-140C column. Unlike many other metal-organic frameworks, MIL-140C is remarkably stable and maintained structure, porosity and performance after five adsorption-desorption cycles., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Ten mixed-linker metal-organic frameworks [Al(OH)(m-BDC-X)(1-y)(m-BDC-SO3H)y] (H2BDC = 1,3-benzenedicarboxylic acid; X = H, NO2, OH) exhibiting the CAU-10-type structure were synthesized. The compounds can be grouped into three series according to the combination of ligands employed. The three series of compounds were obtained by employing different ratios of m-H2 BDC-X and m-H2BDC-SO3Li. The resulting compounds, which are denoted CAU-10-H/Sx, -N/Sx and -O/Sx, show exceptionally high thermal stability for sulfonated materials of up to 350 °C. Detailed characterization with special focus on polarity and acidity was performed, and the impact of the additional SO3H groups is clearly demonstrated by changes in the sorption affinities/capacities towards several gases and water vapor. In addition, selected samples were evaluated for proton conductivity and as catalysts for the gas-phase dehydration of ethanol to ethylene. While only very low proton conductivities were observed, a pronounced increase in catalytic activity was achieved. Although reactions were performed at temperatures of 250 and 300 °C for more than 40 h, no desulfonation and no loss of crystallinity were observed, and stable ethanol conversion resulted. This demonstrates the high stability of this material., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The synthesis of the commercially available aluminum fumarate sample A520 has been optimized and its structure analyzed through a combination of powder diffraction, solid-state NMR spectroscopy, molecular simulation, IR spectroscopy, and thermal analysis. A520 is an analogue of the MIL-53(Al)-BDC solid, but with a more rigid behavior. The differences between the commercial and the optimized samples in terms of defects have been investigated by in situ IR spectroscopy and correlated to their catalytic activity for ethanol dehydration., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The abundant sesquiterpene β-caryophyllene can be epoxidized by molecular oxygen in the absence of any catalyst. In polar aprotic solvents, the reaction proceeds smoothly with epoxide selectivities exceeding 70 %. A mechanistic study has been performed and the possible involvement of free radical, spin inversion, and electron transfer mechanisms is evaluated using experimental and computational methods. The experimental data-including a detailed reaction product analysis, studies on reaction parameters, solvent effects, additives and an electrochemical investigation-all support that the spontaneous epoxidation of β-caryophyllene constitutes a rare case of unsensitized electron transfer from an olefin to triplet oxygen under mild conditions (80 °C, 1 bar O2 ). As initiation of the oxygenation reaction, the formation of a caryophyllene-derived radical cation via electron transfer is proposed. This radical cation reacts with triplet oxygen to a dioxetane via a chain mechanism with chain lengths exceeding 100 under optimized conditions. The dioxetane then acts as an in situ-formed epoxidizing agent. Under nitrogen atmosphere, the presence of a one-electron acceptor leads to the selective isomerization of β-caryophyllene to isocaryophyllene. Observations indicate that this isomerization reaction is a novel and elegant synthetic pathway to isocaryophyllene., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The first microfluidic method for accurately depositing monodisperse single MOF crystals is presented, enabling unprecedented high-throughput, yet flexible single-crystal printing. Individual droplets of MOF precursor solutions are actuated over a matrix of hydrophilic-in-hydrophobic micropatterns for the controlled generation of femtoliter droplets. As such, thousands of monodisperse single MOF crystals are printed per second in a desired pattern, without the use of impractically expensive equipment., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Acid zeolites were screened as heterogeneous catalysts for racemization of benzylic alcohols. The most promising zeolites appeared to be H-Beta zeolites, for which the optimal reaction conditions were studied in further detail. The zeolite performance was compared to that of homogeneous acids and acid resins under similar reaction conditions. In a second part of the research, H-Beta zeolites were applied in dynamic kinetic resolution (DKR) of 1-phenylethanol, which was conducted by means of a two-phase approach and which resulted in yields smoothly crossing the 50% border up to 90%, with an enantiomeric excess of >99%. To explore the applicability of this biphasic methodology, several other substrates were examined in the standard racemization reaction and in the biphasic dynamic kinetic resolution.

Layered double hydroxides (LDHs), exchanged with molybdate, decompose H2O2 to form one molecule of singlet-state dioxygen (1O2) from two molecules of H2O2. The dependence of the kinetics of H2O2 decomposition on Mo and H2O2 concentrations and on temperature has been related to structural characteristics of the material (X-ray diffraction (XRD), scanning electron microscopy (SEM), IR spectroscopy, N2 adsorption, thermogravimetry) and to molybdate speciation as revealed by in-situ studies in the presence of peroxide (FT Raman, diffuse reflectance UV/visible spectroscopy). The H2O2 decomposition rate is linearly correlated with the amount of LDH-exchanged molybdate, except when a considerable fraction of the molybdate occupies less accessible interlayer positions. A maximum in the H2O2 decomposition rate as the H2O2 concentration is increased is due to the successive formation of mono-, di-, tri-, and tetraperoxomolybdates. This behavior was modeled successfully by using the equilibrium constants for formation of the Mo-peroxo complexes, and the rate constants for decay of the peroxomolybdates with 1O2 liberation. Time-resolved diffuse reflectance and Raman observations of the various MoO4(2-)-peroxide adducts are in line with the proposed kinetic scheme. Of all the Mo-peroxo species on the LDH, the triperoxomolybdate has the highest rate for decay to 1O2. Comparison with the kinetics of dissolved molybdate shows that the monomolecular decay of all peroxomolybdate species proceeds much faster at the LDH surface than in solution. Consequently, maximal rates per Mo atom are at least twice as high for the heterogeneous LDH catalyst as for the homogeneous systems.