Evaluation of triphenylene-based MOF ultrathin films for lithium batteries

Metal–organic frameworks (MOFs) are attractive candidates to meet the requirement of next-generation batteries, as functional materials with a high surface area, well-defined metal centers, and organic linkers through coordination bonds. Due to their great tunability, MOFs have been investigated as electrodes or electrolytes in lithium batteries and more recently as protective layers in anode-less batteries. Here, we synthesize a Ni3(HHTP)2 MOF directly at the air–liquid interface of a Langmuir trough and grow the electrode on a conductive substrate by the transference process. The characterization during Langmuir film formation shows that the addition of crystallization time during the compression process enhances the formation of 2D crystalline domains, as observed by in situ grazing-incidence X-ray diffraction. Next, the transferred Ni3(HHTP)2 ultrathin films were studied as working electrodes in Li batteries in a half-cell configuration and compared with bare copper. The results show that the Ni3(HHTP)2 film protects the Cu collector from oxidation, and the negative charge accumulates in the organic ligand during the lithiation process while NiII oxidizes to NiIII, unlike other triphenylene-based MOFs with CuII or CoII metal nodes. The galvanostatic plating–stripping cycles of the batteries show that the inclusion of the crystallization time improves the coulombic efficiency, especially significantly in the first cycles when the SEI is formed. This work shows the Langmuir technique as a useful tool to test MOF based materials for batteries with the advantages of using a low amount of raw materials and without the need to introduce additives (binder and electron conductor) in the electrodes. The electrochemical study of this type of electrode allows a first screening to synthesize electrodes based on MOFs and can be a tool for the preparation of protective coatings under optimized conditions

Improving the gas sorption capacity in lantern-type metal-organic polyhedra by a scrambled cage method

The synthesis of multivariate metal-organic frameworks (MOFs) is a well-known method for increasing the complexity of porous frameworks. In these materials, the structural differences of the ligands used in the synthesis are sufficiently subtle that they can each occupy the same site in the framework. However, multivariate or ligand scrambling approaches are rarely used in the synthesis of porous metal-organic polyhedra (MOPs) – the molecular equivalent of MOFs – despite the potential to retain a unique intrinsic pore from the individual cage while varying the extrinsic porosity of the material. Herein we directly synthesise scrambled cages across two families of lantern-type MOPs and find contrasting effects on their gas sorption properties. In one family, the scrambling approach sees a gradual increase in the BET surface area with the maximum and minimum uptakes associated with the two pure homoleptic cages. In the other, the scrambled materials display improved surface areas with respect to both of the original, homoleptic cages. Through analysis of the gas sorption isotherms, we attribute this effect to the balance of micro- and mesoporosity within the materials, which varies as a result of the scrambling approach. The gas uptake of the materials presented here underscores the tunability of cages that springs from their combination of intrinsic, extrinsic, micro- and meso- porosities

Porous metal-organic cages based on rigid bicyclo[2.2.2]oct-7-ene type ligands : synthesis, structure, and gas uptake properties

Three new ligands containing a bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxydiimide unit have been used to assemble lantern-type metal-organic cages with the general formula [Cu4L4]. Functionalisation of the backbone of the ligands leads to distinct crystal packing motifs between the three cages, as observed with single-crystal X-ray diffraction. The three cages vary in their gas sorption behaviour, and the capacity of the materials for CO2 is found to depend on the activation conditions: softer activation conditions lead to superior uptake, and one of the cages displays the highest BET surface area found for lantern-type cages so far

Improving the gas sorption capacity in lantern-type metal-organic polyhedra by a scrambled cage method.

The synthesis of multivariate metal-organic frameworks (MOFs) is a well-known method for increasing the complexity of porous frameworks. In these materials, the structural differences of the ligands used in the synthesis are sufficiently subtle that they can each occupy the same site in the framework. However, multivariate or ligand scrambling approaches are rarely used in the synthesis of porous metal-organic polyhedra (MOPs) – the molecular equivalent of MOFs – despite the potential to retain a unique intrinsic pore from the individual cage while varying the extrinsic porosity of the material. Herein we directly synthesise scrambled cages across two families of lantern-type MOPs and find contrasting effects on their gas sorption properties. In one family, the scrambling approach sees a gradual increase in the BET surface area with the maximum and minimum uptakes associated with the two pure homoleptic cages. In the other, the scrambled materials display improved surface areas with respect to both of the original, homoleptic cages. Through analysis of the gas sorption isotherms, we attribute this effect to the balance of micro- and mesoporosity with the materials. The gas uptake of the materials presented here underscores the tunability of cages that springs from their combination of intrinsic, extrinsic, micro- and meso- porosities