Tandem Electrooxidation - Reductive Amination of Biobased Isohexides Towards Bicyclic Diamines.

Isohexide-derived diamines are considered preferred precursors for the production of biobased polyurethanes and polyamides. However, current synthesis methods from isohexides suffer from serious issues concerning selectivity and the recyclability of the process auxiliaries (e. g. homogeneous catalysts), which renders a translation to the industry highly unlikely. Here, we report on the production of such diamine building blocks, via a tandem electrooxidation - reductive amination process in which the process auxiliaries can be easily recycled. The application of (immobilized) TEMPO in combination with simple halides (e. g. NaBr) in the electrochemical step even enables the oxidation of the sterically hindered exo-OHs of the isohexides to the corresponding diketones (yield up to 99 %). In the subsequent reductive amination, the produced ketones are atom-efficiently converted to isohexide diamines utilizing NH3, H2, and Ru/C and an acid resin cocatalyst.

Effective and sustainable depolymerization of Nylon 66 - a transamidation for the complete recycling of polyamides.

The transamidation of polyamides with short primary amides is reported as an effective recycling technique. This novel depolymerization method is robust and only utilizes cheap and renewable reagents. The process requires a Nb2O5 catalyst, assisted by NH3, and operates at relatively mild reaction conditions (i.e. 200 °C and 3 bar NH3).

Confined Water Cluster Formation in Water Harvesting by Metal-Organic Frameworks: CAU-10-H versus CAU-10-CH3.

Several metal-organic frameworks (MOFs) excel in harvesting water from the air or as heat pumps as they show a steep increase in water uptake at 10-30 % relative humidity (RH%). A precise understanding of which structural characteristics govern such behavior is lacking. Herein, CAU-10-H and CAU-10-CH3 are studied with H, CH3 corresponding to the functions grafted to the organic linker. CAU-10-H shows a steep water uptake ≈18 RH% of interest for water harvesting, yet the subtle replacement of H by CH3 in the organic linker drastically changes the water adsorption behavior to less steep water uptake at much higher humidity values. The materials' structural deformation and water ordering during adsorption with in situ sum-frequency generation, in situ X-ray diffraction, and molecular simulations are unraveled. In CAU-10-H, an energetically favorable water cluster is formed in the hydrophobic pore, tethered via H-bonds to the framework µï£¿OH groups, while for CAU-10-CH3, such a favorable cluster cannot form. By relating the findings to the features of water adsorption isotherms of a series of MOFs, it is concluded that favorable water adsorption occurs when sites of intermediate hydrophilicity are present in a hydrophobic structure, and the formation of energetically favorable water clusters is possible.

Nanoscale Chemical Diversity of Coke Deposits on Nanoprinted Metal Catalysts Visualized by Tip-Enhanced Raman Spectroscopy.

Coke formation is the prime cause of catalyst deactivation, where undesired carbon wastes block the catalyst surface and hinder further reaction in a broad gamut of industrial chemical processes. Yet, the origins of coke formation and their distribution across the catalyst remain elusive, obstructing the design of coke-resistant catalysts. Here, the first-time application of tip-enhanced Raman spectroscopy (TERS) is demonstrated as a nanoscale chemical probe to localize and identify coke deposits on a post-mortem metal nanocatalyst. Monitoring coke at the nanoscale circumvents bulk averaging and reveals the local nature of coke with unmatched detail. The nature of coke is chemically diverse and ranges from nanocrystalline graphite to disordered and polymeric coke, even on a single nanoscale location of a top-down nanoprinted SiO2 -supported Pt catalyst. Surprisingly, not all Pt is an equal producer of coke, where clear isolated coke "hotspots" are present non-homogeneously on Pt which generate large amounts of disordered coke. After their formation, coke shifts to the support and undergoes long-range transport on the surrounding SiO2 surface, where it becomes more graphitic. The presented results provide novel guidelines to selectively free-up the coked metal surface at more mild rejuvenation conditions, thus securing the long-term catalyst stability.

Metal-Free Electrocatalytic Diacetoxylation of Alkenes.

1,2-Dioxygenation of alkenes leads to a structural motif ubiquitous in organic synthons, natural products and active pharmaceutical ingredients. Straightforward and green synthesis protocols starting from abundant raw materials are required for facile and sustainable access to these crucial moieties. Especially industrially abundant aliphatic alkenes have proven to be arduous substrates in sustainable 1,2-dioxygenation methods. Here, we report a highly efficient electrocatalytic diacetoxylation of alkenes under ambient conditions using a simple iodobenzene mediator and acetic acid as both the solvent and an atom-efficient reactant. This transition metal-free method is applicable to a wide range of alkenes, even challenging feedstock alkenes such as ethylene and propylene, with a broad functional group tolerance and excellent faradaic efficiencies up to 87 %. In addition, this protocol can be extrapolated to alkenoic acids, resulting in cyclization of the starting materials to valuable lactone derivatives. With aromatic alkenes, a competing mechanism of direct anodic oxidation exists which enables reaction under catalyst-free conditions. The synthetic method is extensively investigated with cyclic voltammetry.

Ammonolytic transfer dehydrogenation of amines and amides: a versatile method to valorize nitrogen compounds to nitriles.

The dehydrogenation of amines has been identified as an efficient method for nitrile synthesis. At present, this approach is restricted to (oxidative) dehydrogenations of primary amines, most often with specialized homogeneous catalysts. In this work, amines were transfer dehydrogenated to nitriles using simple and cheap alkenes (e.g. ethylene or propene) as hydrogen scavengers. The scope was expanded to secondary amines, tertiary amines and even aldehydes. Additional nitrogen is built in from NH3. The versatility of the process was proven by coupling it to the ammonolysis of secondary amides. This enabled us to recycle long-chain polyamides (LCPA) into monomeric compounds, i.e. α,ω-amidonitriles and dinitriles. Reactions were performed with a recyclable heterogeneous Pt catalyst, at 200 °C and with limited addition of NH3 and ethylene. High yields of up to 94% were obtained for the corresponding nitriles.

Design of an Organic Template for Synthesizing ITR Zeolites under Ge-Free Conditions.

Germanosilicate zeolites with various structures have been extensively synthesized, but the syntheses of corresponding zeolite structures in the absence of germanium species remain a challenge. One such example is an ITR zeolite structure, which is a twin of the ITH zeolite structure. Through the modification of a classic organic template for synthesizing ITH zeolites and thus designing a new organic template with high compatibility to ITR zeolite assisted by theoretical simulation, we, for the first time, show the Ge-free synthesis of an ITR structure including pure silica, aluminosilicate, and borosilicate ITR zeolites. These materials have high crystallinity, corresponding to an ITR content of more than 95%. In the methanol-to-propylene (MTP) reaction, the obtained aluminosilicate ITR zeolite exhibits excellent propylene selectivity and a long lifetime compared with conventional aluminosilicate ZSM-5 zeolite. The strategy for the design of organic templates might offer a new opportunity for rational syntheses of novel zeolites and, thus, the development of highly efficient zeolite catalysts in the future.

Isopropenyl phosphate as an atom efficient reagent for phosphorylation of alcohols with catalytic base.

The atom efficient transesterification of phosphate esters with catalytic base was investigated using an isopropenyl leaving group, generating acetone as the only by-product. The reaction proceeds in good yields at room temperature, with excellent chemoselectivity towards primary alcohols. Mechanistic insights were obtained by obtaining kinetic data using in operando NMR-spectroscopy.

Cu-α-diimine Compounds Encapsulated in Porous Materials as Catalysts for Electrophilic Amination of Aromatic C-H Bonds.

Electrophilic amination has emerged as a more environmentally benign approach to construct arene C-N bonds. However, heterogeneous catalysts remain largely unexplored in this area, even though their use could facilitate product purification and catalyst recovery. Here we investigate strategies to heterogenize a Cu(2,2'-bipyridine) catalyst for the amination of arenes lacking a directing group with hydroxylamine-O-sulfonic acid (HOSA). Besides immobilization of Cu on a metal-organic framework (MOF) or covalent organic framework (COF) with embedded 2,2'-bipyridines, a ship-in-a-bottle approach was followed in which the Cu complex is encapsulated in the pores of a zeolite. Recyclability and hot centrifugation tests show that zeolite Beta-entrapped CuII(2,2'-bipyridine) is superior in terms of stability. With N-methylmorpholine as a weakly coordinating, weak base, simple arenes, such as mesitylene, could be aminated with yields up to 59%, corresponding to a catalyst TON of 24. The zeolite could be used in three consecutive runs without a decrease in activity. Characterization of the catalyst by EPR and XAS showed that the active catalytic complex consisted of a site-isolated CuII species with one 2,2'-bipyridine ligand.

Adsorptive separation using self-assembly on graphite: from nanoscale to bulk processes.

Adsorptive separation is a promising lower-energy alternative for traditional industrial separation processes. While carbon-based materials have a long history in adsorptive removal of organic contaminants from solution or gas mixtures, separation using an adsorption/desorption protocol is rarely considered. The main drawbacks are the limited control in bulk adsorption experiments, as often all organic molecules are adsorbed, and lack of desorption methods to retrieve the adsorbed molecules. Using high-resolution on-surface characterization with scanning tunneling microscopy (STM), an increased understanding of the on-surface adsorption behavior under different conditions was obtained. The insight obtained from the nanoscale experiments was used to develop a highly selective separation method using adsorption and desorption on graphite, which was tested for the separation of quinonoid zwitterions. These experiments on adsorptive separation using self-assembly on graphite show its potential and demonstrate the advantage of combining surface characterization techniques with bulk experiments to exploit different possible applications of carbon-based materials.

Metal-biomolecule frameworks (BioMOFs): a novel approach for "green" optoelectronic applications.

In this study, a water-stable microcrystalline bioMOF was synthesized, characterized, and loaded with silver ions or highly emissive rare earth (RE) metals such as Eu3+/Tb3+. The obtained materials were used as active layers in a proof-of-concept sustainable light-emitting device, highlighting the potential of bioMOFs in optoelectronic applications.

Ru-Bipyridine Entrapped in the Supercages of EMC-1 Faujasite as Catalyst for the Trifluoromethylation of Arenes.

Trifluoromethyl (CF3) groups are versatile structural motifs especially in the field of agrochemicals and pharmaceuticals. However, current trifluoromethylation reactions are generally associated with stoichiometric amounts of transition metals/metal oxidants, homogeneous catalysts, high temperatures, and expensive trifluoromethylating agents. In this work, the homogeneous photocatalyst Ru(bipy)32+ is entrapped in the pores of a faujasite support (EMC-1) via a "ship-in-a-bottle" strategy. The formation of the coordination compound was confirmed by Fourier transform infrared (FTIR), UV-Vis spectroscopy, and X-ray absorption spectroscopy (XAS). Due to its high stability toward acidified environments, this single-site heterogeneous catalyst is suitable for the trifluoromethylation of synthetically interesting (hetero)arenes under visible-light irradiation at room temperature. Furthermore, the heterogeneous catalyst could efficiently be reused for at least three times with minimal catalyst leaching/deactivation.

From crude industrial waste glycerol to biopropene via Ru-mediated hydrodeoxygenation in ionic liquids.

The catalytic conversion of crude glycerol to biopropene was investigated. A bifunctional Ru-ionic liquid system showed a high tolerance for common crude glycerol impurities like water, salts and methanol. After optimizing both dehydration and olefin selectivity, a 82% biopropene yield (94% selectivity) was obtained directly from industrial waste glycerol.

Heterogeneous Single-Site Catalysts for C-H Activation Reactions: Pd(II)-Loaded S,O-Functionalized Metal Oxide-Bisphosphonates.

Heterogeneous single-site catalysts contain spatially isolated, well-defined active sites. This allows not only their easy recovery by solid-liquid separation but also the detailed active site design similar to homogeneous catalysts. Here, heterogeneous Pd(II) single-site catalysts were assembled, based on mesoporous metal oxide-bisphosphonate materials as supports. This new family of hybrid organic-inorganic materials with tunable porosity was further functionalized with thioether ligands containing S,O-binding sites that enhance the activity of Pd(II) for C-H activation reactions. The structures of the resulting Pd(II) single-site catalysts were carefully analyzed via solid-state NMR spectroscopy, via texture analysis by N2 physisorption, infrared spectroscopy, and transmission electron microscopy. Furthermore, the immediate environment of the isolated Pd(II) active sites was studied with X-ray absorption spectroscopy. A clear relationship between the thioether ligand surface density and catalyst activity could be established. Significantly higher yields were obtained using highly porous metal oxide-bisphosphonate materials as supports compared to materials with lower porosities, such as conventional metal oxides, indicating that the high surface area facilitates the presence of isolated, well-accessible S,O-supported Pd(II) active sites. A wide scope of model substrates, including industrially relevant arenes, can be converted with high yields by the optimal heterogeneous Pd catalyst.

A Cationic Oligomer as an Organic Template for Direct Synthesis of Aluminosilicate ITH Zeolite.

There are a large number of zeolites, such as ITH, that cannot be prepared in the aluminosilicate form. Now, the successful synthesis of aluminosilicate ITH zeolite using a simple cationic oligomer as an organic template is presented. Key to the success is that the cationic oligomer has a strong complexation ability with aluminum species combined with a structural directing ability for the ITH structure similar to that of the conventional organic template. The aluminosilicate ITH zeolite has very high crystallinity, nanosheet-like crystal morphology, large surface area, fully four-coordinated Al species, and abundant acidic sites. Methanol-to-propylene (MTP) tests reveal that the Al-ITH zeolite shows much higher selectivity for propylene and longer lifetime than commercial ZSM-5. FCC tests show that Al-ITH zeolite is a good candidate as a shape-selective FCC additive for enhancing propylene and butylene selectivity.

Highly Selective Removal of Perfluorinated Contaminants by Adsorption on All-Silica Zeolite Beta.

Perfluorinated alkylated substances (PFASs) are widely used in industrial and commercial applications, leading to a widespread occurrence of these persistent and harmful contaminants in our environment. Removal of these compounds from surface and waste waters is being mandated by European and U.S. governments. Currently, there are no treatment techniques available that lower the concentrations of these compounds for large water bodies in a cost- and energy-efficient way. We hereby propose a hydrophobic, all-silica zeolite Beta material that is a highly selective and high-capacity adsorbent for PFASs, even in the presence of organic competitors. Advanced characterization data demonstrate that the adsorption process is driven by a very negative adsorption enthalpy and favorable steric factors.

C2-H Arylation of Indoles Catalyzed by Palladium-Containing Metal-Organic-Framework in γ-Valerolactone.

An efficient and selective procedure was developed for the direct C2-H arylation of indoles using a Pd-loaded metal-organic framework (MOF) as a heterogeneous catalyst and the nontoxic biomass-derived solvent γ-valerolactone (GVL) as a reaction medium. The developed method allows for excellent yields and C-2 selectivity to be achieved and tolerates various substituents on the indole scaffold. The established conditions ensure the stability of the catalyst as well as recoverability, reusability, and low metal leaching into the solution.

Engineering a Highly Defective Stable UiO-66 with Tunable Lewis- Brønsted Acidity: The Role of the Hemilabile Linker.

The stability of metal-organic frameworks (MOFs) typically decreases with an increasing number of defects, limiting the number of defects that can be created and limiting catalytic and other applications. Herein, we use a hemilabile (Hl) linker to create up to a maximum of six defects per cluster in UiO-66. We synthesized hemilabile UiO-66 (Hl-UiO-66) using benzene dicarboxylate (BDC) as linker and 4-sulfonatobenzoate (PSBA) as the hemilabile linker. The PSBA acts not only as a modulator to create defects but also as a coligand that enhances the stability of the resulting defective framework. Furthermore, upon a postsynthetic treatment in H2SO4, the average number of defects increases to the optimum of six missing BDC linkers per cluster (three per formula unit), leaving the Zr-nodes on average sixfold coordinated. Remarkably, the thermal stability of the materials further increases upon this treatment. Periodic density functional theory calculations confirm that the hemilabile ligands strengthen this highly defective structure by several stabilizing interactions. Finally, the catalytic activity of the obtained materials is evaluated in the acid-catalyzed isomerization of α-pinene oxide. This reaction is particularly sensitive to the Brønsted or Lewis acid sites in the catalyst. In comparison to the pristine UiO-66, which mainly possesses Brønsted acid sites, the Hl-UiO-66 and the postsynthetically treated Hl-UiO-66 structures exhibited a higher Lewis acidity and an enhanced activity and selectivity. This is further explored by CD3CN spectroscopic sorption experiments. We have shown that by tuning the number of defects in UiO-66 using PSBA as the hemilabile linker, one can achieve highly defective and stable MOFs and easily control the Brønsted to Lewis acid ratio in the materials and thus their catalytic activity and selectivity.

Unravelling Why and to What Extent the Topology of Similar Ce-Based MOFs Conditions their Photodynamic: Relevance to Photocatalysis and Photonics.

Metal-organic frameworks (MOFs) are emerging materials for luminescent and photochemical applications. Armed with femto to millisecond spectroscopies, and fluorescence microscopy, the photobehaviors of two Ce-based MOFs are unravelled: Ce-NU-1000 and Ce-CAU-24-TBAPy. It is observed that both MOFs show ligand-to-cluster charge transfer reactions in ≈100 and ≈70 fs for Ce-NU-1000 and Ce-CAU-24-TBAPy, respectively. The formed charge separated states, resulting in electron and hole generation, recombine in different times for each MOF, being longer in Ce-CAU-24-TBAPy: 1.59 and 13.43 µs than in Ce-NU-1000: 0.64 and 4.91 µs. The linkers in both MOFs also undergo a very fast intramolecular charge transfer reaction in ≈160 fs. Furthermore, the Ce-NU-1000 MOF reveals excimer formation in 50 ps, and lifetime of ≈14 ns. The lack of this interlinkers event in Ce-CAU-24-TBAPy arises from topological restriction and demonstrates the structural differences between the two frameworks. Single-crystal fluorescence microscopy of Ce-CAU-24-TBAPy shows the presence of a random distribution of defects along the whole crystal, and their impact on the observed photobehavior. These findings reflect the effect of linkers topology and metal clusters orientations on the outcome of electronic excitation of reticular structure, key to their applicability in different fields of science and technology, such as photocatalysis and photonics.

Surfactant-templated zeolites for the production of active pharmaceutical intermediates.

A hierarchical USY zeolite has been produced using the surfactant-templating method and used as a catalyst for the production of two important active pharmaceutical ingredients. The presence of intracrystalline mesoporosity in the zeolite results in a significant increase in both the activity (up to 30 fold increase in TOF) and reusability for Friedel-Crafts alkylation and aldol condensation steps.