Selective Electrochemical Oxygen Reduction to Hydrogen Peroxide by Confinement of Cobalt Porphyrins in a Metal-Organic Framework.

Sustainable alternatives for the energy intensive synthesis of H2O2 are necessary. Molecular cobalt catalysts show potential but are typically restricted by undesired bimolecular pathways leading to the breakdown of both H2O2 and the catalyst. The confinement of cobalt porphyrins in the PCN-224 metal-organic framework leads to an enhanced selectivity towards H2O2 and stability of the catalyst. Consequently, oxygen can now be selectively reduced to hydrogen peroxide with a stable conversion for at least 5 h, illustrating the potential of catalysts confined in MOFs to increase the selectivity and stability of electrocatalytic conversions.

Direct Probing of Vibrational Interactions in UiO-66 Polycrystalline Membranes with Femtosecond Two-Dimensional Infrared Spectroscopy.

UiO-66 is a benchmark metal-organic framework that holds great promise for the design of new functional materials. In this work, we perform two-dimensional infrared measurements on polycrystalline membranes of UiO-66 grown on c-sapphire substrates. We study the symmetric and antisymmetric stretch vibrations of the carboxylate groups of the terephthalate linker ions and find that these vibrations show a rapid energy exchange and a collective vibrational relaxation with a time constant of 1.3 ps. We also find that the symmetric vibration of the carboxylate group is strongly coupled to a vibration of the aromatic ring of the terephthalate ion. We observe that the antisymmetric carboxylate vibrations of different terephthalate linkers show rapid resonant (Förster) energy transfer with a time constant of ∼1 ps.

Correction: Role of additives and solvents in the synthesis of chiral isoreticular MOF-74 topologies.

Correction for 'Role of additives and solvents in the synthesis of chiral isoreticular MOF-74 topologies' by Andreea Gheorghe et al., Dalton Trans., 2021, DOI: 10.1039/D1DT01945G.

Role of additives and solvents in the synthesis of chiral isoreticular MOF-74 topologies.

Chiral induction is a simple and inexpensive approach to synthesise chiral metal-organic frameworks, even when using achiral building-blocks. The challenge lies in selecting the proper chiral inductor. This can only be achieved upon understanding the mechanism behind the chirality transfer from the chiral guest to the achiral MOF. In this work, the role of two types of chiral additives and different solvents was investigated in the crystallization of isoreticular MOF-74. We show that pyrrolidone-based solvents can interact with the framework walls and influence the thermal stability of the MOF. The role of the different chiral additives is related to the strength of their interaction with the MOF. Unlike cinchona alkaloids that have weak interactions with the framework, L- or D-trans-4-hydroxyproline (L- or D-Hyp) can strongly bind to the Zn2+ metal centres and cause the twisting of the organic linker. Moreover, L- and D-Hyp additives can affect the IRMOF-74 nucleation process depending on their concentration and handedness.

Synthesis of Chiral MOF-74 Frameworks by Post-Synthetic Modification by Using an Amino Acid.

The synthesis of chiral metal-organic frameworks (MOFs) is highly relevant for asymmetric heterogenous catalysis, yet very challenging. Chiral MOFs with MOF-74 topology were synthesised by using post-synthetic modification with proline. Vibrational circular dichroism studies demonstrate that proline is the source of chirality. The solvents used in the synthesis play a key role in tuning the loading of proline and its interaction with the MOF-74 framework. In N,N'-dimethylformamide, proline coordinates monodentate to the Zn2+ ions within the MOF-74 framework, whereas it is only weakly bound to the framework when using methanol as solvent. Introducing chirality within the MOF-74 framework also leads to the formation of defects, with both the organic linker and metal ions missing from the framework. The formation of defects combined with the coordination of DMF and proline within the framework leads to a pore blocking effect. This is confirmed by adsorption studies and testing of the chiral MOFs in the asymmetric aldol reaction between acetone and para-nitrobenzaldehyde.

Water-Ethanol and Methanol-Ethanol Separations Using in Situ Confined Polymer Chains in a Metal-Organic Framework.

This study presents a straightforward approach for the in situ polymerization of poly(N-isopropylacrylamide) (PNIPAM) chains within the one-dimensional (1D) pores of the five-coordinated zinc-based metal-organic framework DMOF in order to obtain new MOF-based composites. The loading amount of PNIPAM within DMOF ⊃ PNIPAM composites can be tuned by changing the initial weight ratio between NIPAM, which is the monomer of PNIPAM, and DMOF. The guest PNIPAM chains in the composites block partially the 1D pores of DMOF, thus leading to a narrowed nanospace. The water adsorption studies reveal that the water uptake increased by increasing the loading of PNIPAM in the final DMOF ⊃ PNIPAM composites, indicating that the exposed amide groups of PNIPAM gradually alter the hydrophobicity of pristine DMOF and lead to hydrophilic DMOF ⊃ PNIPAM composites. The composite with the highest loading of PNIPAM displays a selective adsorption for water and methanol over ethanol when using equimolar mixtures of methanol-ethanol and water-ethanol. This is confirmed by the single-component adsorption measurements as well as ideal adsorbed solution theory molecular simulations. Additionally, the water stability of pristine DMOF has been greatly improved after the incorporation of PNIPAM in its pores. PNIPAM can undergo a phase transition between hydrophobic and hydrophilic phases in response to a low temperature change. This property is used in order to control the desorption of water and methanol molecules, thus enabling an efficient and cost-effective regeneration process.

Tuning the supramolecular isomerism of MOF-74 by controlling the synthesis conditions.

Supramolecular isomerism of metal-organic frameworks (MOFs) is known for several MOF structures, having direct implications on the properties of these materials. Although the synthesis of MOF isomers is mainly serendipitous in nature, achieving controlled formation of a target framework is highly relevant for practical applications. This work discusses the influence of additives and synthesis conditions on the formation of porous isomers containing Zn2+ as nodes and 2,5-dihydroxy-1,4-benzenedicarboxylate (dobdc4-) as a linker. Using solvent mixtures containing strongly coordinated molecules, e.g. N,N'-dimethylformamide (DMF) and N-methylpyrrolidone (NMP), facilitates the formation of porous structures of type [Zn2(dobdc)(S)x]·yS (S = DMF, NMP) which are built from dinuclear Zn2(O)2(CO2)3 secondary building units (SBUs) consisting of two different edge-sharing polyhedra with the Zn2+ ions in a unsaturated coordinative environment. In the presence of water, the Zn2+ dimers are converted to one-dimensional infinite Zn2+ chains, in which the number of Zn2+-linker bonds increases, therefore giving a hydrolytically more stable coordination environment. The full characterization of the isomers as well as their conversion to the most stable isomer is presented.

Efficient Separation of Ethanol-Methanol and Ethanol-Water Mixtures Using ZIF-8 Supported on a Hierarchical Porous Mixed-Oxide Substrate.

This work reports a new approach for the synthesis of a zeolitic imidazolate framework (ZIF-8) composite. It employs the direct growth of the crystalline ZIF-8 on a mixed-metal oxide support TiO2-SiO2 (TSO), which mimics the porous structure of Populus nigra. Using the natural leaf as a template, the TSO support was prepared using a sol-gel method. The growth of the ZIF-8 layer on the TSO support was carried out by the seeds and second growth method. This method facilitates the homogeneous dispersion of ZIF-8 crystals at the surface of the TSO composite. The ZIF-8@TSO composite adsorbs methanol selectively, mainly due to the hierarchical porous structure of the mixed oxide support. As compared with the as-synthesized ZIF-8, a 50% methanol uptake is achieved in the ZIF-8@TSO composite, with only 25 wt % ZIF-8 loading. IAST simulations show that the ZIF-8@TSO composite has a preferential adsorption toward methanol when using an equimolar methanol-ethanol mixture. An opposite behavior is observed for the as-synthesized ZIF-8. The results show that combining MOFs and mixed-oxide supports with bioinspired structures opens opportunities for synthesizing new materials with unique and enhanced adsorption and separation properties.

Coordination polymers from alkaline-earth nodes and pyrazine carboxylate linkers.

A new series of alkaline-earth-metal based coordination polymers were synthesized by using a pyrazine-2,5-dicarboxylic acid (2,5-H2pzdc) ligand under hydrothermal conditions. These compounds show a variety of structural topologies, reflecting the variable coordination geometries of the alkaline-earth ions as well as the key role of the metal precursor salts. Ca, Sr, and Ba give porous three-dimensional compounds, namely [Ca(2,5-pzdc)(H2O)2]·H2O (1), [Sr(2,5-pzdc)(H2O)4]·H2O (3), [Ba(2,5-pzdc)(H2O)4]·2H2O (4) and [Ba(2,5pzdc)(H2O)2] (5), that feature one-dimensional hydrophilic channels which are filled with water molecules. The Sr compound retains its structure when the lattice water molecules are removed, while the other compounds undergo a structural rearrangement. The hydrophilicity of the Sr compound combined with its high stability even in the absence of guest molecules are the key characteristics that determine its good water adsorption and proton conductivity properties.

Sustainable Separations of C4 -Hydrocarbons by Using Microporous Materials.

Petrochemical refineries must separate hydrocarbon mixtures on a large scale for the production of fuels and chemicals. Typically, these hydrocarbons are separated by distillation, which is extremely energy intensive. This high energy cost can be mitigated by developing materials that can enable efficient adsorptive separation. In this critical review, the principles of adsorptive separation are outlined, and then the case for C4 separations by using zeolites and metal-organic frameworks (MOFs) is examined. By analyzing both experimental and theoretical studies, the challenges and opportunities in C4 separation are outlined, with a focus on the separation mechanisms and structure-selectivity correlations. Zeolites are commonly used as adsorbents and, in some cases, can separate C4 mixtures well. The pore sizes of eight-membered-ring zeolites, for example, are in the order of the kinetic diameters of C4 isomers. Although zeolites have the advantage of a rigid and highly stable structure, this is often difficult to functionalize. MOFs are attractive candidates for hydrocarbon separation because their pores can be tailored to optimize the adsorbate-adsorbent interactions. MOF-5 and ZIF-7 show promising results in separating all C4 isomers, but breakthrough experiments under industrial conditions are needed to confirm these results. Moreover, the flexibility of the MOF structures could hamper their application under industrial conditions. Adsorptive separation is a promising viable alternative and it is likely to play an increasingly important role in tomorrow's refineries.

Dual-mode humidity detection using a lanthanide-based metal-organic framework: towards multifunctional humidity sensors.

Combined photoluminescence and impedance spectroscopy studies show that a europium-based metal-organic framework behaves as a highly effective and reliable humidity sensor, enabling dual-mode humidity detection.

Water-Dispersible Silica-Coated Upconverting Liposomes: Can a Thin Silica Layer Protect TTA-UC against Oxygen Quenching?

Light upconversion by triplet-triplet annihilation (TTA-UC) in nanoparticles has received considerable attention for bioimaging and light activation of prodrugs. However, the mechanism of TTA-UC is inherently sensitive for quenching by molecular oxygen. A potential oxygen protection strategy is the coating of TTA-UC nanoparticles with a layer of oxygen-impermeable material. In this work, we explore if (organo)silica can fulfill this protecting role. Three synthesis routes are described for preparing water-dispersible (organo)silica-coated red-to-blue upconverting liposomes. Their upconversion properties are investigated in solution and in A549 lung carcinoma cells. Although it was found that the silica offered no protection from oxygen in solution and after uptake in A549 cancer cells, upon drying of the silica-coated liposome dispersion in an excess of (organo)silica precursor, interesting liposome-silica nanocomposite materials were obtained that were capable of generating blue light upon red light excitation in air.

A rational synthesis of hierarchically porous, N-doped carbon from Mg-based MOFs: understanding the link between nitrogen content and oxygen reduction electrocatalysis.

Controlled mixtures of novel Mg-based metal-organic frameworks (MOFs) were prepared, with H(+) or K(+) as counterions. A linear relation was found between synthesis pH and K/H ratio in the resultant mixture, establishing the tunability of the synthesis. Upon pyrolysis, these precursor mixtures yield nitrogen-doped, hierarchically porous carbons, which have good activity towards the oxygen reduction reaction (ORR) at pH 13. The nitrogen content varies significantly along the homologous carbon series (>400%, 1.3 at% to 5.7 at%), to a much greater extent than microstructural parameters such as surface area and graphitization. This allows us to isolate the positive correlation between nitrogen content and electrocatalytic oxygen reduction ORR activity in this class of metal-free, N-doped, porous carbons.

Mixed-Lanthanoid Metal-Organic Framework for Ratiometric Cryogenic Temperature Sensing.

A ratiometric thermometer based on a mixed-metal Ln(III) metal-organic framework is reported that has good sensitivity in a wide temperature range from 4 to 290 K and a quantum yield of 22% at room temperature. The sensing mechanism in the europium-doped compound Tb0.95Eu0.05HL (H4L = 5-hydroxy-1,2,4-benzenetricarboxylic acid) is based not only on phonon-assisted energy transfer from Tb(III) to Eu(III) centers, but also on phonon-assisted energy migration between neighboring Tb(III) ions. It shows good performance in a wide temperature range, especially in the range 4-50 K, reaching a sensitivity up to 31% K(-1) at 4 K.

A novel one-dimensional chain built of vanadyl ions and pyrazine-2,5-dicarboxylate.

We present a new coordination polymer, {[VO(pzdc)(H2O)2] H2O}n, built from vanadyl and pyrazine-2,5-dicarboxylate (pzdc) ions. It consists of a one-dimensional chain of vanadyl ions linked by pzdc ions. The carboxylate groups show monodentate coordination, while the pyrazine ring is present both in non-coordinated and coordinated modes. This novel structure is stabilized by an intricate network of hydrogen bonds. The material is highly robust, and thermally stable up to 400 K. It is also antiferromagnetic, with a maximum magnetic susceptibility at ca. 50 K. The orbital shape and population analysis by means of DFT analysis confirm the π-acceptor role of the aromatic nitrogen function of the ligand, while the oxygen-based moieties (carboxylates from pzdc, the aqua ligands and oxo from V=O group) behave as normal donors. Charting the density flow related with significant transitions computed by time-dependent DFT, we determined the ligand-to-metal charge transfer processes. The topology of the chain complex implies two different types of connecting bridges. Using Broken Symmetry DFT modelling gives evidence for two different exchange coupling mechanisms between the vanadyl ions along each of these two molecular bridges. One is strongly antiferromagnetic, practically reducing the chain to 'vanadyl dimers'. The other is almost uncoupled, due to the large distance between the vanadyl ions.

Highly selective water adsorption in a lanthanum metal-organic framework.

We present a new metal-organic framework (MOF) built from lanthanum and pyrazine-2,5-dicarboxylate (pyzdc) ions. This MOF, [La(pyzdc)1.5(H2O)2]⋅2 H2O, is microporous, with 1D channels that easily accommodate water molecules. Its framework is highly robust to dehydration/hydration cycles. Unusually for a MOF, it also features a high hydrothermal stability. This makes it an ideal candidate for air drying as well as for separating water/alcohol mixtures. The ability of the activated MOF to adsorb water selectively was evaluated by means of thermogravimetric analysis, powder and single-crystal X-ray diffraction and adsorption studies, indicating a maximum uptake of 1.2 mmol g(-1) MOF. These results are in agreement with the microporous structure, which permits only water molecules to enter the channels (alcohols, including methanol, are simply too large). Transient breakthrough simulations using water/methanol mixtures confirm that such mixtures can be separated cleanly using this new MOF.

Synthesis, characterization and testing of a new V2O5/Al2O3-MgO catalyst for butane dehydrogenation and limonene oxidation.

We report the synthesis and characterization of new V2O5/Al2O3-MgO catalysts and their application in oxidative dehydrogenation and epoxidation reactions. The materials were prepared by wet impregnation under excess acid conditions. Anchoring of the desired species on the support occurs via an exchange reaction between the vanadium complex and surface hydroxyl groups. The IR and UV-Vis spectra of these catalysts indicate the presence of monomeric vanadium species at 5 wt% V2O5 loading, along with small amounts of polymeric species at 5 and 10 wt% V2O5 loadings. Electron paramagnetic resonance (EPR) spectroscopy reveals the presence of ferromagnetic VO(2+) dimers following calcination at 773 K. The catalysts were then tested in two reactions, namely the gas phase oxidative dehydrogenation of n-butane under flow conditions at 773 K and the liquid phase epoxidation of limonene with H2O2. The dehydrogenation reaction gave butenes and 1,3-butadiene in moderate selectivity at 8-10% conversion. The epoxidation of limonene was less successful, giving 50-70% selectivity to the 1,2-epoxide at 10-20% conversion.

Poly(vinylidene fluoride)/nickel nanocomposites from semicrystalline block copolymer precursors.

The fabrication of nanoporous poly(vinylidene fluoride) (PVDF) and PVDF/nickel nanocomposites from semicrystalline block copolymer precursors is reported. Polystyrene-block-poly(vinylidene fluoride)-block-polystyrene (PS-b-PVDF-b-PS) is prepared through functional benzoyl peroxide initiated polymerization of VDF, followed by atom transfer radical polymerization (ATRP) of styrene. The crystallization of PVDF plays a dominant role in the formation of the block copolymer structure, resulting in a spherulitic superstructure with an internal crystalline-amorphous lamellar nanostructure. The block copolymer promotes the formation of the ferroelectric ß-polymorph of PVDF. Selective etching of the amorphous regions with nitric acid leads to nanoporous PVDF, which functions as a template for the generation of PVDF/Ni nanocomposites. The lamellar nanostructure and the ß-crystalline phase are conserved during the etching procedure and electroless nickel deposition.

Mononuclear and dinuclear manganese compounds stabilized by supramolecular interactions.

New manganese compounds [Mn(HphpzMe)(2)(H(2)phpzMe)(HCO(2))] (1), [Mn(2)(phpzMe)(2)(HphpzMe)(2)(OCH(3))]·2CH(3)OH (2), Na{[Mn(HphpzPh)(phpzPh)(MeOH)(2)](2)}(HCO(2)) (3), [Mn(HphpzPh)(2)(EtOH)(2)]ClO(4)·2EtOH (4) and [Mn(HphpzPh)(2)N(3)] (5) were synthesized and characterized with various techniques. 1, 4 and 5 are mononuclear manganese(III) compounds, 2 is a mixed-valence dinuclear manganese(III/IV) compound, and 3 is a trinuclear compound containing two manganese(III) ions and a sodium(I) ion. A remarkable feature is the spontaneous formation of the formate ion as a result of the methanol or methoxide oxidation in compounds 1 and 3. Using ethanol precludes the formation of the formate and compound 4 is obtained. The molecular structure of all compounds is stabilized by supramolecular interactions, including strong hydrogen bonding and π-π interactions.

Structure and magnetism in Fe-Gd based dinuclear and chain systems. The interplay of weak exchange coupling and zero field splitting effects.

The synthesis and characterization of two Fe-Gd systems based on bpca(-) (Hbpca = bis(2-pyridilcarbonyl)amine) as bridging ligand is presented, taking the systems as a case study for structure-property correlations. Compound 1, [Fe(LS)(II)(µ-bpca)(2)Gd(NO(3))(2)(H(2)O)]NO(3)·2CH(3)NO(2), is a zigzag polymer, incorporating the diamagnetic low spin Fe(LS)(II) ion. The magnetism of 1 is entirely determined by the weak zero field splitting (ZFS) effect on the Gd(III) ion. Compound 2 is a Fe(III)-Gd(III) dinuclear compound, [Fe(LS)(III)(bpca)(µ-bpca)Gd(NO(3))(4)]·4CH(3)NO(2)·CH(3)OH, its magnetism being interpreted as due to the antiferromagnetic coupling between the S(Fe) = ½ and S(Gd) = 7/2 spins, interplayed with the local ZFS on the lanthanide center. In both systems, the d-f assembly is determined by the bridging capabilities of the ambidentate bpca(-) ligand, which binds the d ion by a tridentate moiety with nitrogen donors and the f center by the diketonate side. We propose a spin delocalization and polarization mechanism that rationalizes the factors leading to the antiferromagnetic d-f coupling. Although conceived for compound 2, the scheme can be proposed as a general mechanism. The rationalization of the weak ZFS effects on Gd(III) by multiconfiguration and spin-orbit ab initio calculations allowed us to determine the details of the small but still significant anisotropy of Gd(III) ion in the coordination sites of compounds 1 and 2. The outlined methodologies and generalized conclusions shed new light on the field of gadolinium coordination magnetochemistry.