Impact of the metal centre (Al³⁺, Fe³⁺) on the post-synthetic lithiation of functionalized MIL-53s and the electrochemical properties of lithiated derivatives

Abstract

Metal-Organic Frameworks (MOFs) combining both organic and inorganic redox-active moieties have recently found their interest in the field of the electrochemical energy storage. We here focused our attention on MIL-53(M)...

Fe(iii)-carboxythiolate layered metal–organic frameworks with interest as active materials for rechargeable alkali-ion batteries

“…Hence, the expected electrochemical process involving the iron (reduction) requests the intercalation of additional alkali ions to maintain the charge balance, while the removal of the pristine sodium would require an oxidation necessarily centred on the organic moieties. At this stage it should be recalled that several salts and coordination polymers based on DOBDC have already demonstrated their interest as positive electrode materials for both Li-and Na-ion batteries with an electrochemical activity associated with the quinone/phenolate redox couple, [46][47][48][49][50][51] but to the best of our knowledge there is currently no report on the sulphur-based analogue DSBDC. The electrochemical activity of Na {Fe(DSBDC)} was evaluated in half-cells with alkali metals as counter electrodes, under galvanostatic conditions, starting with a reduction (see the Experimental section for details).…”

Expanding the horizons of porphyrin metal–organic frameworks via catecholate coordination: exploring structural diversity, material stability and redox properties

“…Coordination to a highly charged cation such as Al(III) also further increases the redox potential by inductive This journal is © The Royal Society of Chemistry 2023 effects. 117,118 Nevertheless, this redox activity is found to be almost irreversible upon further reduction and cycling, indicating that this solid is not suited for reversible electrochemical energy storage. CatPMOF-3(In) presents a similar behavior during the rst oxidation, with two marked plateaus at 3.45 and 3.7 V vs. Li + /Li, accounting each for ∼0.6 electrons per catecholate unit.…”