Bridging the Green Gap: Metal–Organic Framework Heteromultilayers Assembled from Porphyrinic Linkers Identified by Using Computational Screening

In organic photovoltaics, porphyrins (PPs) are among the most promising compounds owing to their large absorption cross-section, wide spectral range, and stability. Nevertheless, a precise adjustment of absorption band positions to reach a full coverage of the so-called green gap has not been achieved yet. We demonstrate that a tuning of the PP Q- and Soret bands can be carried out by using a computational approach for which substitution patterns are optimized in silico. The most promising candidate structures were then synthesized. The experimental UV/Vis data for the solvated compounds were in excellent agreement with the theoretical predictions. By attaching further functionalities, which allow the use of PP chromophores as linkers for the assembly of metal-organic frameworks (MOFs), we were able to exploit packing effects resulting in pronounced redshifts, which allowed further optimization of the photophysical properties of PP assemblies. Finally, we use a layer-by-layer method to assemble the PP linkers into surface-mounted MOFs (SURMOFs), thus obtaining high optical quality, homogeneous and crystalline multilayer films. Experimental results are in full accord with the calculations, demonstrating the huge potential of computational screening methods in tailoring MOF and SURMOF photophysical properties.     

Copper-based metal–organic framework decorated by CuO hair-like nanostructures: Electrocatalyst for oxygen evolution reaction

We report a Cu-based metal–organic framework (MOF) decorated by CuO nanostructures as an efficient catalyst for the oxygen evolution reaction (OER). MIL-53(Cu) was synthesized by a hydrothermal approach using 1,4-bezenedicarboxylic acid as organic precursor and further annealed at 300°C to form CuO nanostructures on its surface. The produced electrocatalyst, CuO@MIL-53(Cu), was characterized using various techniques. Under alkaline conditions, the developed electrocatalyst exhibited an overpotential of 801 and 336 mV versus RHE at 10 and 1 mA cm⁻², respectively. The reproducibility of the catalytic performance was validated using several electrodes. It was confirmed that the CuO hair-like nanostructures grown on MIL-53(Cu) using thermal treatment exhibit high OER activity, good kinetics and durability. CuO@MIL-53(Cu) is an economic noble-metal-free OER electrocatalyst. It has potential for application as anode material for sustainable energy technologies like batteries, fuel cells and water electrolysis.     

Metal–Organic Framework (MOF)-Derived Carbon-Mediated Interfacial Reaction for the Synthesis of CeO2−MnO2 Catalysts

CeO₂-based catalysts are widely studied in catalysis fields. Developing one novel synthetic approach to increase the intimate contact between CeO₂ and secondary species is of particular importance for enhancing catalytic activities. Herein, an interfacial reaction between metal–organic framework (MOF)-derived carbon and KMnO₄ to synthesize CeO₂−MnO₂, in which carbon is derived from the pyrolysis of Ce-MOFs under an inert atmosphere, is described. The MOF-derived carbon is found to restrain the growth of CeO₂ crystallites under a high calcination temperature and, more importantly, intimate contact within CeO₂/C is conveyed to CeO₂/MnO₂ after the interfacial reaction; this is responsible for the high catalytic activity of CeO₂−MnO₂ towards CO oxidation.     

An Ion-Exchangeable MOF with Reversible Dehydration and Dynamic Structural Behavior (NH4)2[Zn2(O3PCH2CH2COO)2]⋅5 H2O (BIRM-1)

(NH₄)₂[Zn₂(O₃PCH₂CH₂COO)₂]⋅5 H₂O (BIRM-1) is a new metal phosphonate material, synthesized through a simple hydrothermal reaction between zinc nitrate and 3-phosphonopropionic acid, using urea and tetraethylammonium bromide as the reaction medium. In common with other metal–organic framework materials, BIRM-1 has a large three-dimensional porous structure providing potential access to a high internal surface area. Unlike most others, it has the advantage of containing ammonium cations within the pores and has the ability to undergo cation exchange. Additionally, BIRM-1 also exhibits a reversible dehydration behavior involving an amorphization-recrystallization cycle. The ability to undergo ion exchange and dynamic structural behavior are of interest in their own right, but also increase the range of potential applications for this material. Here the crystal structure of this new metal phosphonate and its ion exchange behavior with K⁺ as an exemplar are studied in detail, and its unusual structure-reviving property reported.     

Efficient Gating of Ion Transport in Three‐Dimensional Metal–Organic Framework Sub‐Nanochannels with Confined Light‐Responsive Azobenzene Molecules

1D nanochannels modified with responsive molecules are fabricated to replicate gating functionalities of biological ion channels, but gating effects are usually weak because small molecular gates cannot efficiently block the large channels in the closed states. Now, 3D metal–organic framework (MOF) sub‐nanochannels (SNCs) confined with azobenzene (AZO) molecules achieve efficient light‐gating functionalities. The 3D MOFSNCs consisting of a MOF UiO66 with ca. 9–12 Å cavities connected by ca. 6 Å triangular windows work as angstrom‐scale ion channels, while confined AZO within the MOF cavities function as light‐driven molecular gates to efficiently regulate the ion flux. The AZO‐MOFSNCs show good cyclic gating performance and high on–off ratios up to 17.8, an order of magnitude higher than ratios observed in conventional 1D AZO‐modified nanochannels (1.3–1.5). This work provides a strategy to develop highly efficient switchable ion channels based on 3D porous MOFs and small responsive molecules.     

Rational Design of a Uranyl Metal–Organic Framework for the Capture and Colorimetric Detection of Organic Dyes

A new uranyl containing metal–organic framework, RPL-1 : [(UO₂)₂(C₂₈H₁₈O₈)] ^. H₂O (RPL for Radiochemical Processing Laboratory), was prepared, structurally characterized, and the solid-state photoluminescence properties explored. Single crystal X-ray diffraction data reveals the structure of RPL - 1 consists of two crystallographically unique three dimensional, interpenetrating nets with a 4,3-connected tbo topology. Each net contains large pores with an average width of 22.8 Å and is formed from monomeric, hexagonal bipyramidal uranyl nodes that are linked via 1,2,4,5-tetrakis(4-carboxyphenyl)benzene (TCPB) ligands. The thermal and photophysical properties of RPL-1 were investigated using thermogravimetric analysis and absorbance, fluorescence, and lifetime spectroscopies. The material displays excellent thermal stability and temperature dependent uranyl and TCPB luminescence. The framework is stable in aqueous media and due to the large void space (constituting 76 % of the unit cell by volume) can sequester organic dyes, the uptake of which induces a visible change to the color of the material.     

Metal–Organic Framework/PVDF Composite Membranes with High H2 Permselectivity Synthesized by Ammoniation

Herein we report a new ammoniation‐based chemical modification strategy for synthesis of continuous and uniform metal–organic framework (MOF)/polyvinylidene fluoride (PVDF) membranes with attractive performance. Ammoniation can promote the support PVDF membrane to produce amino groups, form a nanoparticle structure, and be well cross‐linked; therefore, the high‐density heterogeneous nucleation sites for MOFs growth were provided and the thermal stability and chemical resistance of composite membranes can be greatly improved. The high‐quality layers of representative Cu‐BTC and ZIF‐8 were synthesized on the chemically modified PVDF membranes. By ammoniation, ZIF‐7 can even be grown under harsh synthetic conditions such as in DMF precursor solutions at 403 K. The fabricated MOF/PVDF composite membranes with excellent hollow fiber structures and enhanced structural stability exhibited high H₂ permselectivities for H₂/CO₂ and H₂/N₂.     

Continuous‐Flow Microwave Synthesis of Metal–Organic Frameworks: A Highly Efficient Method for Large‐Scale Production

Metal–organic frameworks are having a tremendous impact on novel strategic applications, with prospective employment in industrially relevant processes. The development of such processes is strictly dependent on the ability to generate materials with high yield efficiency and production rate. We report a versatile and highly efficient method for synthesis of metal–organic frameworks in large quantities using continuous flow processing under microwave irradiation. Benchmark materials such as UiO‐66, MIL‐53(Al), and HKUST‐1 were obtained with remarkable mass, space–time yields, and often using stoichiometric amounts of reactants. In the case of UiO‐66 and MIL‐53(Al), we attained unprecedented space–time yields far greater than those reported previously. All of the syntheses were successfully extended to multi‐gram high quality products in a matter of minutes, proving the effectiveness of continuous flow microwave technology for the large scale production of metal–organic frameworks.     

The First One‐Pot Synthesis of Metal–Organic Frameworks Functionalised with Two Transition‐Metal Complexes

The synthesis of a metal–organic framework (UiO‐67) functionalised simultaneously with two different transition metal complexes (Ir and Pd or Rh) through a one‐pot procedure is reported for the first time. This has been achieved by an iterative modification of the synthesis parameters combined with characterisation of the resulting materials using different techniques, including X‐ray absorption spectroscopy (XAS). The method also allows the first synthesis of UiO‐67 with a very wide range of loadings (from 4 to 43 mol %) of an iridium complex ([IrCp*(bpydc)(Cl)Cl]^2?; bpydc=2,2′‐bipyridine‐5,5′‐dicarboxylate, Cp*=pentamethylcyclopentadienyl) through a pre‐functionalisation methodology.     

A Porous Sulfonated 2D Zirconium Metal–Organic Framework as a Robust Platform for Proton Conduction

By using the strategy of pre-assembly chlorosulfonation applied to a linker precursor, the first sulfonated zirconium metal–organic framework ( JUK-14 ) with two-dimensional (2D) structure, was synthesized. Single-crystal X-ray diffraction reveals that the material is built of Zr₆O₄(OH)₄(COO)₈ oxoclusters, doubly 4-connected by angular dicarboxylates, and stacked in layers spaced 1.5 nm apart by the presence of sulfonic groups. JUK-14 exhibits excellent hydrothermal stability, permanent porosity confirmed by gas adsorption studies, and shows high (>10⁻⁴ S/cm) and low (<10⁻⁸ S/cm) proton conductivity under humidified and anhydrous conditions, respectively. Post-synthesis inclusion of imidazole improves the overall conductivity increasing it to 1.7×10⁻³ S/cm at 60 °C and 90 % relative humidity, and by 3 orders of magnitude at 160 °C. The combination of 2D porous nature with robustness of zirconium MOFs offers new opportunities for exploration of the material towards energy and environmental applications.