Air pollution causes the premature death of ca. 7 million people each year, with SOx gases being among the most harmful contaminants. Reducing the sulfur content in liquid fossil fuels is crucial for overcoming this health and environmental issue. Among the different available technologies, photooxidative desulfurization (PODS) stands out as one of the most promising methods, since it only requires sunlight to drive the reaction. Metal-Organic Frameworks (MOFs), with their tunable porosity and chemical diversity, have emerged as potential adsorbents and photocatalysts for the removal of sulfur-containing compounds from fuels. In this work, the reactivity of the ligand 2,5-disulfhydrylbenzene-1,4-dicarboxylic acid (H4DSBDC) with different V salts was evaluated to prepare new photocatalytically active metal-organic frameworks. Two new compounds, labeled (DMA)KVIVO(DSBDC) and MIL-47(VIII)-(SCH3)2, were successfully synthesized via solvothermal methods. X-Ray diffraction structural analysis revealed that the second solid relies exclusively on V-O bonds, whereas both V-O and V-S bonds are found in the first one. Both MOFs are stable in suspension and absorb light in the visible region, prompting their evaluation as photocatalysts for visible-light-driven reactions. For the first time, V-based metal-organic frameworks are proposed for the photooxidative desulfurization reaction. Among them, MIL-47(V)-(SCH3)2 demonstrated superior performance, achieving a desulfurization efficiency of 73%, which was maintained for at least 4 consecutive cycles.

Polyacrylic acid (PAA) is an emerging binder for silicon-graphite (Si-Gr) composite anodes due to its strong affinity for the native SiOx layer that covers Si particles and its ability to act as an artificial solid-electrolyte interphase (SEI). Here, PAA with a high molecular weight (Mw = 845 kg mol(-1)) is synthesized using a green, aqueous route. The effect of varying PAA content (from similar to 3 to 15wt%) on electrode processing, physical properties, and cycling stability is systematically investigated. Increasing PAA concentration improves slurry stability and dispersion, widening the electrode processability window. X-ray photoelectron spectroscopy (XPS) confirms that PAA preferentially localizes on the silicon surface, with evidence of agglomeration at higher concentrations. An optimal PAA content of 10.6 wt% delivers the highest reversible specific capacity and good cycling stability (1270 mAh gelectrode(-1) at the 50th cycle in half cell and 860 mAh g(electrode)(-1) in full cell). Lower PAA content results in deficient binder networks and increased irreversible capacity, while excessive binder content leads to binder agglomeration and increased resistivity. Post-mortem solid-state NMR analysis further supports the role of PAA as an artificial SEI, mitigating uncontrolled electrolyte decomposition and lithium loss.

Catalytic CO2 hydrogenation to CH4 is an important field of research that aims to achieve net-zero emissions. Conventional processes use high temperatures (> 350 degrees C) and pressures (>20 bar) to overcome the high energy barriers of this kinetically demanding eight-electron reduction reaction. Even though some studies have reported the photocatalytic version of this reaction under milder reaction conditions, the temperatures commonly used are still between 200 and 300 degrees C and pressures up to 20 bar. This paper reports on an engineered mixed-metal porphyrinic metal-organic framework MIL-173(Zr/Ti) decorated RuOx nanoparticles to catalyse this reaction at low temperatures (125 to 175 degrees C) and pressure (1.5 bar) under simulated sunlight irradiation. The performance of this material at 175 degrees C (reaching up to 1.63 mmol CH4 g(-1) h(-1), with apparent quantum yields (AQYs) ranging from 3.2 at 400 nm to 1% at 700 nm) ranks it among the most active MOF-based photocatalysts reported so far under similar reaction conditions. These AQY values are also higher or comparable than to other reported solid photocatalysts, even when they operate at temperatures in the range between 200 and 250 degrees C. Insights about materials performance were experimentally obtained using several techniques, including nanosecond transient absorption spectroscopy, photoluminescence, transient photocurrent, electrochemical impedance spectroscopy and thermal imaging together with additional photocatalytic tests. RuOx@MIL-173(Zr/Ti) activity can be explained by the multifunctionality of this photocatalyst favoring chemisorption of reagents, a wide range of visible light absorption, efficient charge separation and photothermal performance.

The growing demand for high-performance lithium-ion (Li-ion) batteries, from portable electronics to electric vehicles, requires efficient thermal management systems to ensure safety, enhance performance, and extend operational lifespan. Conventional solutions remain limited by scalability, low energy density, and thermal instability, motivating the search for innovative materials. Here, we present a fully characterized, scalable, and multifunctional solid-solid phase change material (SS-PCM), bis(n-dodecylammonium) tetrachlorocuprate (C12Cu), engineered for passive thermal regulation in Li-ion batteries. C12Cu is synthesized at the kilogram scale and exhibits a solid-solid transition near 55 degrees C with a latent heat of similar to 72 J g(-1) and thermal stability up to 150 degrees C in air. Comprehensive characterization reveals pseudoplastic rheology, reversible elastic softening, moderate intrinsic thermal conductivity (similar to 0.3 W m(-1) K-1), and excellent dielectric strength (6 kV mm(-1)), enabling additive-free shaping by compression molding. We further demonstrate the first proof of concept for integrating this intrinsic SS-PCM into an imitation Li-ion battery mini-module, where C12Cu reduced peak temperatures by 11 degrees C under high-power (3C) cycling compared to a conventional ABS-based system. These results position C12Cu as a scalable, moldable, and application-viable SS-PCM platform for next-generation battery safety and thermal performance.

Solid-solid phase change materials (SS-PCMs) are attractive candidates for thermal energy storage (TES) owing to their intrinsic shape stability, yet their widespread application remains limited by the lack of design rules linking the molecular structure to phase-transition properties. Here, we present a comprehensive study of layered hybrid chlorometallates, (C n H 2n+1 NH3)2MCl4 (M = Cu, Mn, Zn; n = 6-16), as tunable SS-PCMs. For that, 15 compounds (M = Cu, Mn, Zn; n = 6, 7, 12, 13, 16) were prepared, and their low-temperature (LT) forms were studied by single-crystal XRD and vibrational spectroscopies. By a multitechnique approach, involving calorimetry, temperature-dependent infrared, and Raman spectroscopies, and combined in a single synchrotron experiment temperature-dependent X-ray absorption spectroscopy (XAS), total scattering/Pair Distribution Function (PDF), and powder XRD (PXRD) analyses, we evidenced the impact of both parameters (M and n) not only on the LT structures but also on the thermal properties and on the high-temperature (HT) structures. Especially, we evidenced that although materials based on octahedrally (here Mn and Cu) and tetrahedrallly (here Zn) coordinated cations share many common features in their LT forms (alternating organic-inorganic layered structures, alkylammonium chains parallel to each other, and supramolecular organic-inorganic interactions of the same nature and strength), their HT phases strongly differ, especially at a medium range distance. This comprehensive study is not only of fundamental interest but will also help to address questions, such as the shaping and mechanical integrity of these SS-PCMs upon thermal cycling that need to be answered prior to their integration into practical devices for next-generation TES.

In this study, we conducted a comprehensive investigation relating to the efficiency of the Al-MOF CAU-10 as a sorbent in a Sorption Enhanced Reaction Process (SERP) based on its hydrophilic/hydrophobic balance. We confirmed both experimentally and through simulation that CAU-10 is a hydrophobic material at low pressure, whereas it shows a high affinity for methanol. The cosorption of water and methanol shows that both molecules are in competition, mostly for the oxygen atoms of the ligands. An important result is the influence of the relative pressure of the vapor mixture on the composition of the adsorbed phase. At low relative pressure, methanol is mostly adsorbed from the mixture, while water is only adsorbed from 0.16 p/p°. At higher relative pressures, water becomes predominant in the adsorbed phase. We therefore took advantage of this result to improve the catalytic reduction of CO2 into methanol by sorption of methanol or water. The catalytic test was performed at 270 °C under a total pressure of 50 bar. Under these conditions, the methanol yield increased by more than 6% compared to a catalytic reaction performed without sorbent, thus validating our fundamental approach.

Silicon is a promising active material for Li-ion battery negative electrodes because of its high theoretical specific capacity as compared to the standard graphite materials (3579 mAh/g vs 372 mAh/g). However, the capacity retention of Si-based anodes is negatively impacted by the Si expansion during lithiation (up to ~300% for Li 15 Si 4 compared to ~10% for LiC 6 ) and subsequent contraction during delithiation. The primary sources of this capacity fade are the delamination of the anode material from the current collector, the isolation of active material, and uncontrolled solid electrolyte interphase (SEI) formation. A resilient polymer binder network can help mitigate the effects of the expansion and contraction of silicon particles and prolong the cycle life of Si-based electrodes. Polyacrylic acid (PAA) is a prevalent binder material for Si-based and Si-Graphite composite electrodes that features carboxylic acid functional groups, which can bind to the native silanol layer on silicon particles. It is known to increase the adhesion of the electrode to the current collector and the cohesion strength of the bulk electrode, as well as act as an artificial SEI layer. The present study aims to optimize the PAA binder formulation in respect to several key parameters, namely its neutralisation degree, substituting cation, polymer molecular weight, and coverage ratio. Previous work from our group on silicon-graphite composite electrodes with a partially neutralized PAA binder yielded promising results. In fact, the simple addition of metal hydroxide has the double effect of increasing the slurry pH and forming carboxylate groups along the polymer chains. The former brings the active materials further away from their isoelectric points (pH ≈ 2.35 for silicon and pH ≈ 4 for graphite), preventing flocculation, while the latter increases interactions between the polymer chains through carboxylate-cation attractive interactions. The strength of these interactions depends on their nature. Monovalent metal cations (Na + , Li + ) promote weaker dipole interactions while polyvalent cations (Mg 2+ , Zn 2+ , Ca 2+ ) create stronger coordination bonds. These interactions have been shown to improve the mechanical properties of the dried electrodes, as well as their capacity retention over cycling in previous studies. Furthermore, the predominant trend in literature is to use a commercially available, high-molecular weight PAA for electrochemical studies. However, these long polymer chains require a more intensive synthesis process and run the risk of folding in on themselves due to intramolecular interactions, especially after the addition of polyvalent cations. Shorter chains are easier to synthesize but are typically thought to be less effective as binders due to their small size compared to the active material particles. High-, intermediate- and low-molecular weight PAA binders are compared in this study to verify these hypotheses. In a final step, an ideal polymer coverage ratio – a compromise between capacity retention and energy density – is determined for each binder formulations. The impact of each of these binder parameters is explored through a variety of characterisation techniques carried out at each electrode processing and testing step. The relative adsorption of each polymer formulation during the slurry dispersion step is studied by gel permeation chromatography. Next, the rheological properties of each slurry under shearing are compared, namely the viscosity, which relates to slurry milling and tape-casting conditions, and the storage and loss moduli, which affect the slurry stability and the electrode coating homogeneity. Next, the mechanical properties of the electrodes are determined by nanoindentation and the coating resistivities are measured with a 4-point probe. The electrochemical performances are ultimately compared to identify optimal binder characteristics for increased capacity retention. In sum, the impacts of the PAA chain length and partial neutralisation through the addition of various metal hydroxides are elucidated. Ideal coverage ratios are also determined for each formulation and an optimized, PAA-based binder for silicon-graphite composite electrodes is highlighted. References: Obrovac, M. N. Si-Alloy Negative Electrodes for Li-Ion Batteries. Curr. Opin. Electrochem. 2018 , 9 , 8–17. https://doi.org/10.1016/j.coelec.2018.02.002. Meyssonnier, C.; Merabet, A.; Dupré, N.; Paireau, C.; Lestriez, B. Critical Binder‐to‐Powders Coverage Ratio for Faster Graphite/SiOx Electrode Formulation Optimization. Small Methods 2024 , 8 (8), 2301370. https://doi.org/10.1002/smtd.202301370. Vanpeene, V.; Huet, L.; Villanova, J.; Olbinado, M.; Marone, F.; Maire, E.; Roué, L.; Devic, T.; Lestriez, B. Deciphering the Benefits of Coordinated Binders in Si‐Based Anodes by Combined Operando/In Situ and Ex Situ X‐Ray Micro‐ and Nano‐Tomographies. Adv. Energy Mater. 2024 , 2403741. https://doi.org/10.1002/aenm.202403741. Jiang, H.; Wei, C.; Yasmin, S.; Obrovac, M. N. Deconvoluting Slurry Rheology from Binder Performance in Si-Based Anodes. J. Electrochem. Soc. 2023 , 170 (12), 120522. https://doi.org/10.1149/1945-7111/ad136f.

In the quest for sustainable and metal-free energy storage systems, viologen-based materials offer exciting prospects as they are synthetically well accessible and show two reversible electrochemical processes with anion insertion. This study introduces and compares two pi-extended viologen-carboxylate materials bearing double zwitterionic backbones as model compounds based on 1,1 '-bis(4-carboxyphenyl)-4,4 '-bipyridinium ([bcbp]): the neutral [bcbp] as a double zwitterionic molecule ( 1 ) and its corresponding (Li)2[bcbp](ClO4)2 disalt ( 2 ). The choice of these two materials for our electrochemical studies is motivated by the literature available on their synthesis routes and solid-state properties. Electrochemical tests in lithium half-cells revealed that compound ( 1 ) is initially inactive but gradually converts into the electroactive disalt ( 2 ) via spontaneous chemical insertion of LiClO4 from the electrolyte. Compound ( 2 ) directly displays the expected reversible two-electron p-type mechanism involving perchlorate anion (de)insertion, while lithium ions act as spectator species. The system delivers stable cycling performance and high coulombic efficiency, supporting the interest of viologen-based zwitterionic salts as host material for negative electrode application in anionic rocking-chair organic batteries. The bipyridinium-bis(carboxylate) radical ((Li)[bcbp]center dot ( 3 )) formed during our synthesis optimizations is likewise electrochemically assessed. This fundamental work highlights the tunability of double zwitterionic viologens as molecular platforms to promote optimized p-type negative electrode materials.

A novel three-dimensional metal-organic framework (MOF) based on magnesium and the triazine triphosphonate ligand has been successfully synthesized via the solvothermal method and fully characterized. Denoted as IEF-31 (IEF stands for IMDEA energy framework), its crystal structure was unveiled by single-crystal X-ray diffraction, exhibiting free P-OH groups in two coordination modes (-PO3H2 and -PO3H) and an open framework with 1D channels (8 × 7 Å). This robust structure shows high thermal and chemical stability (in several catalytic-relevant organic solvents and water, pH = 2 to 10). Further, this study presents the proof of concept for using an Mg-based P-MOF as a catalyst in the ring-opening polymerization of ε-caprolactone (ε-CL) with relevance in the challenging bioplastic formation. Specifically, IEF-31(Mg) achieved notable monomer conversions and polymer molecular weights with low dispersity values (Đ ≈ 1.1), paving the way for further design and optimization of robust, efficient, and sustainable Mg P-MOFs for clean polymerization processes.

Slurry solid fraction is often treated as an innocuous battery electrode processing parameter at the laboratory scale. In fact, articles that put a number to the water content of their slurries are few and far between. However, recent studies from our group have shown that the slurry solid fraction can have a significant impact on the electrochemical performances of the resulting electrodes. The present research aims to highlight the importance of optimising this parameter by demonstrating its impact throughout the electrode preparation and testing processes of Si-graphite electrodes for Li-ion batteries. Silicon, graphite, a conductive additive of graphene nanoplatelet (GnP) and a partially neutralized PAA-based binder (PAH 0.8 Na 0.2 , pH ≈ 4, M w = 1084k, 393k or 7.6k g/mol) were dispersed in a variable amount of deionized water, yielding slurries of different solid fractions according to equation 1: Eq. 1 SF = (m Si + m Gr + m GnP ) / m Slurry An initial impact of the slurry solid fraction can be seen in the adsorption of the binder onto the active material and conductive additive in aqueous conditions. Gel permeation chromatography of the polymer remaining in the liquid phase after slurry dispersion reveals a strong preferential adsorption of high-molecular weight PAA, mainly on the silicon particles, that is even more pronounced at higher solid fraction. This localized polymer distribution affects its ability to fulfill its functions as a binder and an artificial solid-electrolyte interphase (SEI), which can later be seen in the irreversible capacity loss that arises from both electrical disconnections and SEI formation during cycling. The solid fraction is also a principal determinant of the rheological properties of the slurry, namely its viscosity under shearing and storage and loss moduli. Shear-thinning behavior is favourable to ensure homogeneous dispersion of matter in the electrode slurry and avoid creating surface defects during the coating process. Increasing the solid fraction leads to shear-thickening behavior in slurries with high-molecular weight binders. As such, large agglomerates of silicon and multiple surface defects are observed in these electrodes. On the other hand, the storage and loss moduli of the slurry will determine its stability during the drying process where there is a risk of sedimentation. The effects of the slurry solid fraction can also be seen in the dried electrodes. For example, the mechanical properties (hardness, elasticity) of the electrodes made with low-solid fraction slurries are comparatively poor, as measured by nanoindentation. Conversely, 4-point probe testing shows that electrodes made with high-solid fraction slurries are more resistive due to the presence of large silicon particles covered in a high concentration of polymer. The numerous impacts of the slurry solid fraction across the electrode preparation and testing processes culminate in a strong dependence of the resulting electrochemical performances on this often-neglected parameter. An optimal solid fraction is determined for the given materials. Formulations with different binder molecular weights are also compared at different solid fractions to illustrate the importance of this optimization step in drawing accurate and meaningful conclusions on the materials at study. References: Ligneel, E.; Lestriez, B.; Hudhomme, A.; Guyomard, D. Effects of the Solvent Concentration (Solid Loading) on the Processing and Properties of the Composite Electrode. J. Electrochem. Soc. 2007 , 154 (3), A235. https://doi.org/10.1149/1.2431316. Porcher, W.; Lestriez, B.; Jouanneau, S.; Guyomard, D. Design of Aqueous Processed Thick LiFePO 4 Composite Electrodes for High-Energy Lithium Battery. J. Electrochem. Soc. 2009 , 156 (3), A133. https://doi.org/10.1149/1.3046129. Xiong, J.; Dupré, N.; Mazouzi, D.; Guyomard, D.; Roué, L.; Lestriez, B. Influence of the Polyacrylic Acid Binder Neutralization Degree on the Initial Electrochemical Behavior of a Silicon/Graphite Electrode. ACS Appl. Mater. Interfaces 2021 , 13 (24), 28304–28323. https://doi.org/10.1021/acsami.1c06683.

Here, we report a rare example of an Fe-based MOF capable of accommodating K+ ions electrochemically within its layered framework, achieving low polarization, high capacity utilization (∼0.8 electrons exchanged per Fe), and stable cycling performance. In situ Mössbauer spectroscopy and operando XRD analyses revealed that the observed electrochemical storage arises from the Fe3+/Fe2+ redox couple with polyphasic transformations.

This study examines the adsorption properties of MIL-120(Al) for pure vapour-phase sorbates (water and methanol) and their mixtures, with a particular focus on the material's selectivity influenced by relative pressure. The selected MOF presents 1-D channels of similar to 3.5 x 6 angstrom(2) aperture, associated with a specific surface area of 350 m(2)/g and a pore volume of 0.26 cm(3)/g. Adsorption isotherms at 25 degrees C, supported by Grand Canonical Monte Carlo (GCMC) simulations, revealed a high affinity of MIL-120(Al) for water and methanol at relative pressures lower than 0.2. However, methanol was identified as the preferred adsorbate at these low relative pressures in water-methanol mixtures. This selectivity, confirmed by GCMC, showed that the composition of the adsorbed phase was made of 90 % of methanol, regardless of the equilibrium vapour phase composition. In contrast, at higher relative pressures, the selectivity of MIL-120(Al) shifted markedly towards water, thereby highlighting the sensitivity of MIL-120(Al) to relative pressure in competitive adsorption scenarios. At high relative pressure, the composition of the adsorbed phase was found to be more than 95 % molar of water, even for vapours mixtures made of 50 % methanol. These findings contribute valuable insights into the design of pressure-sensitive adsorption systems for industrial applications such as sorption enhanced reaction production (SERP) technology.

The simple addition of a Zn(II) precursor to a preoptimized poly(carboxylic acid) binder solution enhances the electrochemical performance and cycle life of silicon-based electrodes. The binder/cation couple forms a cross-linked coordinated binder that plays a key role in enhancing the mechanical and chemical stability of the electrode microstructure. The impact of the addition of the Zn precursor on the microstructural evolution of the electrode during cycling is investigated at different scales (from cell/electrode to silicon particle scale) using complementary operando, in situ, and ex situ X-ray tomography techniques. Comparative analyses conducted on the reference and with Zn electrode formulations using operando and in situ X-ray micro-tomography allow for monitoring of the electrode morphological deformations along with the crack pattern formation and evolution during cycling. The benefits of the precursor addition include enhancing the mechanical stability of the electrode through a strengthened microstructure more apt to maintaining its integrity, as well as a better anchoring to the current collector leading to decreased electrical disconnections and capacity fade. Moreover, complementary ex situ X-ray nano-tomography measurements highlight the benefits of the precursor addition in terms of chemical stability with mitigated solid electrolyte interface (SEI) formation over the electrode cycling. The benefits of a simple, yet efficient, method to boost the mechanical and chemical stability of Si-based electrode microstructure through the addition of a Zn(II) precursor to a carboxylic binder is demonstrated thanks to a cross-correlated multiscale workflow based on operando/in situ and ex situ X-ray tomography analyses. image

Isoreticularity is one of the key aspects in the design of new Metal-Organic Frameworks (MOFs), but has been up to now scarcely applied to gallate (1,2-3-trioxobenzene) ligands. With the aim of building new materials isoreticular to the M(Hngal) (H4gal = gallic acid) small pore MOF series, we here designed the new elongated mixed gallate-carboxylate ligand 4-(3,4,5-trihydroxyphenyl)benzoic acid (H4bpgal). A thorough investigation of its reactivity with MgCl2 has led to the successful isolation of the targeted material Mg(H2bpgal)center dot n(solv) (solv = water, methanol, ethanol). A combination of experimental tools, including single-crystal X-ray diffraction (XRD), powder XRD, and 1H and 13C solid-state NMR studies confirmed the close structural relationship with the smaller analogue, including the presence of acidic OH sites arising from phenol groups bound to Mg cations. Contrary to the small pore analogue, Mg(H2bpgal) is of limited interest for gas capture, because of its moderate stability upon exposure to dioxygen and low affinity for CO2, both resulting from the intrinsic characteristics of the ligand (redox activity and flexibility, respectively). Nevertheless, it presents among the highest surface area and pore volume reported to date for a gallate MOF (1475 m2 g-1 and 0.59 cm3 g-1, respectively); these characteristics might be of interest in other fields of applications, including electrochemical energy storage or combined controlled drug release.

An enlarged version of the ubiquitous tetrathiafulvalene-tetrabenzoic acid is described, with 4,4'-biphenyl moieties as spacers between the coordination moieties and the electroactive core. The obtained rectangular ligand has a 14 × 22 Å2 size and is combined with Zn(II) under solvothermal conditions to yield a coordination polymer endowed with large cavities of ca. 15 × 11 Å2/10 × 10 Å2. The topology of the material is discussed in detail using the Points of Extension and Metals (PE&M) or the Straight-rod (STR) representation, and the sqc1121 or tfo topological type of the structure is observed, respectively. Its stability towards solvent removal and electrical properties are discussed. The material does not present any permanent porosity upon desolvation according to nitrogen sorption measurements at 77 K. Nevertheless, a significant increase in conductivity is observed on compressed pellets of the material upon post-synthetic oxidation with iodine. Raman spectroscopy combined with density functional theory (DFT) calculations has been used to characterize the oxidation state of tetrakis(4-carboxylic acid biphenyl)tetrathiafulvalene for coordination polymers.

Porphyrinic metal-organic frameworks (MOFs) offer high surface areas and tunable catalytic and optoelectronic properties, making them versatile candidates for applications in phototherapy, drug delivery, photocatalysis, electronics, and energy storage. However, a key challenge for industrial integration is the rapid, cost-effective production of suitable sizes. This study introduces Zr(IV) alkoxides as metal precursors, achieving ultrafast (∼minutes) and high-yield (>90%) synthesis of three well-known Zr-based porphyrinic MOF nanocrystals: MOF-525, PCN-224, and PCN-222, each with distinct topologies. By adjusting linker-to-metal and modulator-to-metal ratios, we attain precise control over single-phase formation. Demonstrating alkoxides’ potential, we synthesized nanosized PCN-224 at room temperature within seconds using a continuous multifluidic method. This advancement greatly simplifies porphyrinic MOF production, enabling broader industrial and scientific applications.

Abstract Sodium‐ion batteries (NIBs) are gaining momentum, thanks to the increasing demand for energy storage devices and the abundant reserves and low sodium cost. Transition metals are well‐established materials due to their high conductivity and electrochemical activity. In this work, metal selenides (MSex) (M: Ni, Co, Fe) are obtained by facile selenization in a single step of transition gallic acid based metal organic frameworks (MOFs) under Ar flow at 600 °C. As the powders undergo selenization, the resulting MSex particles are encapsulated within the amorphous carbon network formed by the decomposition of the gallate ligand. The microstructures are examined by HR‐TEM analyses and the characteristic interplanar spacing of each transition metal selenide is measured and found to coincide with the XRD pattern. Meanwhile, the specific surface areas were measured as 121, 152, and 155 m2/g for CoSe2, NiSe and FeSe, respectively. The resulting NiSe/C, CoSe2/C and FeSe/C nanomaterials are tested as NIB negative electrodes and are shown to have a capacity of 315, 312, and 363 mAh/g, respectively, after 100 cycles at a current density of 100 mA/g while Na‐ion diffusion coefficients (DNa+) are calculated in the range of 10−10–10−7 cm2/s by galvanostatic intermittent titration (GITT) technique.

MIL-53(M)-(OH) 2 (M = Al, Fe) solids based on a redox active dioxoterephthalate ligand were lithiated post-synthesis, and the resulting products were evaluated as positive electrode materials for Li-ion batteries.

Porphyrin based Metal-Organic Frameworks (MOFs) have generated high interest because of their unique combination of light absorption, electron transfer and guest adsorption/desorption properties. In this study, we expand the range of available MOF materials by focusing on the seldom studied porphyrin ligand H10TcatPP, functionalized with tetracatecholate coordinating groups. A systematic evaluation of its reactivity with M(iii) cations (Al, Fe, and In) led to the synthesis and isolation of three novel MOF phases. Through a comprehensive characterization approach involving single crystal and powder synchrotron X-ray diffraction (XRD) in combination with the local information gained from spectroscopic techniques, we elucidated the structural features of the solids, which are all based on different inorganic secondary building units (SBUs). All the synthesized MOFs demonstrate an accessible porosity, with one of them presenting mesopores and the highest reported surface area to date for a porphyrin catecholate MOF (>2000 m2 g-1). Eventually, the redox activity of these solids was investigated in a half-cell vs. Li with the aim of evaluating their potential as electrode positive materials for electrochemical energy storage. One of the solids displayed reversibility during cycling at a rather high potential (∼3.4 V vs. Li+/Li), confirming the interest of redox active phenolate ligands for applications involving electron transfer. Our findings expand the library of porphyrin-based MOFs and highlight the potential of phenolate ligands for advancing the field of MOFs for energy storage materials.