Direct Synthesis of MOF-74 Materials on Carbon Fiber Electrodes for Structural Supercapacitors.

The use of fossil fuels has contributed significantly to environmental pollution and climate change. For this reason, the development of alternative energy storage devices is key to solving some of these problems. The development of lightweight structures can significantly reduce the devices' weight, thereby reducing energy consumption and emissions. Combining lightweight structures with alternative energy storage technologies can further improve efficiency and performance, leading to a cleaner and more sustainable system. In this work, for the first time, MOF-74 materials with different divalent metal ions have been synthesized directly on carbon fiber, one of the most widely used materials for the preparation of electrodes for supercapacitors with structural properties. Different techniques, such as nitrogen adsorption-desorption isotherms, cyclic voltammetry or galvanostatic charge-discharge, among others, were used to evaluate the influence of the metal cation on the electrochemical capacitance behavior of the modified electrodes. The Co-MOF-74 material was selected as the best modification of the carbon fibers for their use as electrodes for the fabrication of structural supercapacitors. The good electrochemical performance shown after the incorporation of MOF materials on carbon fibers provides a viable method for the development of carbon fiber electrodes, opening a great variety of alternatives.

MOF-808 as an Efficient Catalyst for Valorization of Biodiesel Waste Production: Glycerol Acetalization.

Glycerol is the main residue in the biodiesel production industry; therefore, their valorization is crucial. The acetalization of glycerol toward fuel additives such as solketal (2,2-dimethyl-1,3-dioxolan-4-methanol) is of high interest, promoting circular economy since it can be added to biodiesel or even fossil diesel to improve their quality and efficiency. Straightforward-prepared metal-organic framework (MOF) materials of the MOF-808 family were applied to the valorization of glycerol for the first time. In particular, MOF-808(Hf) was revealed to be an effective heterogeneous catalyst to produce solketal under moderate conditions: a small amount of the MOF material (only 4 wt% of glycerol), a 1:6 ratio of glycerol/acetone, and a temperature of 333 K. The high efficiency of MOF-808(Hf) was associated with the high amount of acid centers present in its structure. Furthermore, its structural characteristics, such as window opening cavity size and pore diameters, were shown to be ideal for reusing this material for at least ten consecutive reaction cycles without losing activity (conversion > 90% and selectivity > 98%). Remarkably, it was not necessary to wash or activate the MOF-808(Hf) catalyst between cycles (no pore blockage occurred), and it maintained structural integrity after ten cycles, confirming its ability to be a sustainable heterogeneous catalyst for glycerol valorization.

Strontium-Based MOFs Showing Dual Emission: Luminescence Thermometers and Toluene Sensors.

This work reports on the preparation and optical characterization of two metal-organic frameworks (MOFs) based on strontium ions and 2-amino-1,4-benzenedicarboxylate (NH2-bdc) ligand: i.e., [Sr(NH2-bdc)(DMF)]n (1) and {[Sr(NH2-bdc)(Form)]·H2O}n (2) (where DMF = dimethylformamide and Form = formamide). Compound 1 has a 3D architecture built up from the linkage established by NH2-bdc among metal-carboxylate rods, leaving significant microchannels that are largely occupied by DMF molecules coordinated to strontium centers. The solvent molecules play a crucial role in the photoluminescence (PL) properties, which has been deeply characterized by diffuse reflectance and variable-temperature emission. Interestingly, both materials present intriguing photoluminescence (PL) properties involving intense short-lived and long-lasting phosphorescence (LLP), though the latter is especially remarkable for compound 2 with a lifetime of 815 ms at low temperature. Conversely, the strong PL shown by 1 may be successfully exploited due to both its luminescent thermochromism observed in the RT to 10 K range and its solvent-dependent PL sensing capacity, imbuing this material with potential activity as a PL thermometer as well as a toluene detector in water solutions.

Two Isostructural URJC-4 Materials: From Hydrogen Physisorption to Heterogeneous Reductive Amination through Hydrogen Molecule Activation at Low Pressure.

Herein, two novel isostructural metal-organic frameworks (MOFs) M-URJC-4 (M = Co, Ni; URJC = "Universidad Rey Juan Carlos") with open metal sites, permanent microposity, and large surface areas and pore volumes have been developed. These novel MOFs, with polyhedral morphology, crystallize in the monoclinic P21/c space group, exhibiting a three-dimensional structure with microporous channels along the c axis. Initially, they were fully characterized and tested in hydrogen (H2) adsorption at different conditions of temperature and pressure. The physisorption capacities of both materials surpassed the gravimetric H2 uptake shown by most MOF materials under the same conditions. On the basis of the outstanding adsorption properties, the Ni-URJC-4 material was used as a catalyst in a one-pot reductive amination reaction using various carbonyl compounds and primary amines. A possible chemical pathway to obtain secondary amines was proposed via imine formation, and remarkable performances were accomplished. This work evidences the dual ability of M-URJC-4 materials to be used as a H2 adsorbent and a catalyst in reductive amination reactions, activating molecular H2 at low pressures for the reduction of C═N double bonds and providing reference structural features for the design of new versatile heterogeneous materials for industrial application.

A double basic Sr-amino containing MOF as a highly stable heterogeneous catalyst.

A novel metal-organic framework (MOF) based on strontium alkaline-earth metal and 2-amino-1,4-benzenedicarboxylic acid (NH2-bdc) has been developed. This material is formed by a linear succession of face-sharing strontium polyhedra bridged by an organic ligand molecule to give a three-dimensional network with rhombohedral one-directional channels. This MOF is stable in polar organic solvents and up to 250 °C. The basic catalytic activity of both strontium metal nodes and amino groups of the ligand was tested in Knoevenagel condensation reactions. The influence of the temperature and reaction solvent over the catalytic performance of the MOF catalyst was demonstrated. The strontium/amino-containing MOF material evidenced a remarkable activity as compared to other conventional alkaline oxides typically used as reference basic solid catalysts. The novel MOF material showed remarkable activity and structural stability during five consecutive catalytic runs with no evidence of activity loss under the best reaction conditions found in this study.

Novel and Versatile Cobalt Azobenzene-Based Metal-Organic Framework as Hydrogen Adsorbent.

A novel URJC-3 material based on cobalt and 5,5'-(diazene-1,2-diyl)diisophthalate ligand, containing Lewis acid and basic sites, has been synthesized under solvothermal conditions. Compound URJC-3, with polyhedral morphology, crystallizes in the tetragonal and P43 21 2 space group, exhibiting a three-dimensional structure with small channels along a and b axes. This material was fully characterized, and its hydrogen adsorption properties were estimated for a wide range of temperatures (77-298 K) and pressures (1-170 bar). The hydrogen storage capacity of URJC-3 is quite high in relation to its moderate surface area, which is probably due to the confinement effect of hydrogen molecules inside its reduced pores of 6 Å, which is close the ionic radii of hydrogen molecules. The storage capacity of this material is not only higher than that of active carbon and purified single-walled carbon nanotubes, but also surpasses the gravimetric hydrogen uptake of most MOF materials.

A Recyclable Cu-MOF-74 Catalyst for the Ligand-Free O-Arylation Reaction of 4-Nitrobenzaldehyde and Phenol.

The activity and recyclability of Cu-MOF-74 as a catalyst was studied for the ligand-free C-O cross-coupling reaction of 4-nitrobenzaldehyde (NB) with phenol (Ph) to form 4-formyldiphenyl ether (FDE). Cu-MOF-74 is characterized by having unsaturated copper sites in a highly porous metal-organic framework. The influence of solvent, reaction temperature, NB/Ph ratio, catalyst concentration, and basic agent (type and concentration) were evaluated. High conversions were achieved at 120 °C, 5 mol % of catalyst, NB/Ph ratio of 1:2, DMF as solvent, and 1 equivalent of K2CO3 base. The activity of Cu-MOF-74 material was higher than other ligand-free copper catalytic systems tested in this study. This catalyst was easily separated and reused in five successive runs, achieving a remarkable performance without significant porous framework degradation. The leaching of copper species in the reaction medium was negligible. The O-arylation between NB and Ph took place only in the presence of Cu-MOF-74 material, being negligible without the solid catalyst. The catalytic advantages of using nanostructured Cu-MOF-74 catalyst were also proven.

New URJC-1 Material with Remarkable Stability and Acid-Base Catalytic Properties.

Emerging new metal-organic structures with tunable physicochemical properties is an exciting research field for diverse applications. In this work, a novel metal-organic framework Cu(HIT)(DMF)0.5, named URJC-1, with a three-dimensional non-interpenetrated utp topological network, has been synthesized. This material exhibits a microporous structure with unsaturated copper centers and imidazole⁻tetrazole linkages that provide accessible Lewis acid/base sites. These features make URJC-1 an exceptional candidate for catalytic application in acid and base reactions of interest in fine chemistry. The URJC-1 material also displays a noteworthy thermal and chemical stability in different organic solvents of different polarity and boiling water. Its catalytic activity was evaluated in acid-catalyzed Friedel⁻Crafts acylation of anisole with acetyl chloride and base-catalyzed Knoevenagel condensation of benzaldehyde with malononitrile. In both cases, URJC-1 material showed very good performance, better than other metal organic frameworks and conventional catalysts. In addition, a remarkable structural stability was proven after several consecutive reaction cycles.