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MIL-53 Metal-Organic Framework as a Flexible Cathode for Lithium-Oxygen Batteries.

ABSTRACT: Li-air batteries possess higher specific energies than the current Li-ion batteries. Major drawbacks of the air cathode include the sluggish kinetics of the oxygen reduction (OER), high overpotentials and pore clogging during discharge processes. Metal-Organic Frameworks (MOFs) appear as promising materials because of their high surface areas, tailorable pore sizes and catalytic centers. In this work, we propose to use, for the first time, aluminum terephthalate (well known as MIL-53) as a flexible air cathode for Li-O₂ batteries. This compound was synthetized through hydrothermal and microwave-assisted routes, leading to different particle sizes with different aspect ratios. The electrochemical properties of both materials seem to be equivalent. Several behaviors are observed depending on the initial value of the first discharge capacity. When the first discharge capacity is higher, no OER occurs, leading to a fast decrease in the capacity during cycling. The nature and the morphology of the discharge products are investigated using ex situ analysis (XRD, SEM and XPS). For both MIL-53 materials, lithium peroxide Li₂O₂ is found as the main discharge product. A morphological evolution of the Li₂O₂ particles occurs upon cycling (stacked thin plates, toroids or pseudo-spheres).

SUBMITTER: Zhang Y

PROVIDER: S-EPMC8399480 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Thermodynamics of the Flexible Metal-Organic Framework Material MIL-53(Cr) From First Principles.

Project description:We use first-principles density functional theory total energy and linear response phonon calculations to compute the Helmholtz and Gibbs free energy as a function of temperature, pressure, and cell volume in the flexible metal-organic framework material MIL-53(Cr) within the quasiharmonic approximation. GGA and metaGGA calculations were performed, each including empirical van der Waals (vdW) forces under the D2, D3, or D3(BJ) parameterizations. At all temperatures up to 500 K and pressures from -30 MPa to 30 MPa, two minima in the free energy versus volume are found, corresponding to the narrow pore (np) and large pore (lp) structures. Critical positive and negative pressures are identified, beyond which there is only one free energy minimum. While all results overestimated the stability of the np phase relative to the lp phase, the best overall agreement with experiment is found for the metaGGA PBEsol+RTPSS+U+J approach with D3 or D3(BJ) vdW forces. For these parameterizations, the calculated free energy barrier for the np-lp transition is only 3 to 6 kJ per mole of Cr4(OH)4(C8H4O4)4.

| S-EPMC5497523 | biostudies-literature

Electrically Induced Breathing of the MIL-53(Cr) Metal-Organic Framework.

Project description:The breathing behavior of the MIL-53(Cr) metal-organic framework (MOF) has been explored previously upon guest-adsorption and thermal and mechanical stimuli. Here, advanced molecular simulations based on the use of an accurate force field to describe the flexibility of this porous framework demonstrate that the application of an electrical field induces the structural switching of this MOF leading to a first-order transition and a volume change of more than 40%. This motivated us to electrically tune the pore size of MIL-53(Cr) with the idea to propose a new concept to selectively capture CO2 over CH4 via a molecular sieving that paves the way toward the optimization of current separation-based processes.

| S-EPMC5445524 | biostudies-literature

Elucidating the Vibrational Fingerprint of the Flexible Metal-Organic Framework MIL-53(Al) Using a Combined Experimental/Computational Approach.

Project description:In this work, mid-infrared (mid-IR), far-IR, and Raman spectra are presented for the distinct (meta)stable phases of the flexible metal-organic framework MIL-53(Al). Static density functional theory (DFT) simulations are performed, allowing for the identification of all IR-active modes, which is unprecedented in the low-frequency region. A unique vibrational fingerprint is revealed, resulting from aluminum-oxide backbone stretching modes, which can be used to clearly distinguish the IR spectra of the closed- and large-pore phases. Furthermore, molecular dynamics simulations based on a DFT description of the potential energy surface enable determination of the theoretical Raman spectrum of the closed- and large-pore phases for the first time. An excellent correspondence between theory and experiment is observed. Both the low-frequency IR and Raman spectra show major differences in vibrational modes between the closed- and large-pore phases, indicating changes in lattice dynamics between the two structures. In addition, several collective modes related to the breathing mechanism in MIL-53(Al) are identified. In particular, we rationalize the importance of the trampoline-like motion of the linker for the phase transition.

| S-EPMC5808359 | biostudies-literature

Experimental Evidence of Negative Linear Compressibility in the MIL-53 Metal-Organic Framework Family.

Project description:We report a series of powder X-ray diffraction experiments performed on the soft porous crystals MIL-53(Al) and NH2-MIL-53(Al) in a diamond anvil cell under different pressurization media. Systematic refinements of the obtained powder patterns demonstrate that these materials expand along a specific direction while undergoing total volume reduction under an increase in hydrostatic pressure. The results confirm for the first time the Negative Linear Compressibility behaviour of this family of materials recently predicted from quantum chemical calculations.

| S-EPMC4338503 | biostudies-literature

A Bimetallic Organic Framework with Mn in MIL-101(Cr) for Lithium-Sulfur Batteries.

Project description:Lithium-sulfur batteries (LSBs) show excellent performance in terms of specific capacity and energy density. However, the cyclic stability of LSBs is compromised due to the "shuttle effect", which hinders the practical applications of LSBs. Herein, a metal-organic framework (MOF) based on Cr ions as the main body composition, commonly known as MIL-101(Cr), was utilized to minimize the shuttle effect and improve the cyclic performance of LSBs. To obtain MOFs with a certain adsorption capacity for lithium polysulfide and a certain catalytic capacity, we propose an effective strategy of incorporating sulfur-loving metal ions (Mn) into the skeleton to enhance the reaction kinetics at the electrode. Based on the oxidation doping method, Mn2+ was uniformly dispersed in MIL-101(Cr) to produce bimetallic Cr2O3/MnOx as a novel sulfur-carrying cathode material. Then, a sulfur injection process was carried out by melt diffusion to obtain the sulfur-containing Cr2O3/MnOx-S electrode. Moreover, an LSB assembled with Cr2O3/MnOx-S showed improved first-cycle discharge (1285 mAh·g-1 at 0.1 C) and cyclic performance (721 mAh·g-1 at 0.1 C after 100 cycles), and the overall performance was much better than that of monometallic MIL-101(Cr) as a sulfur carrier. These results revealed that the physical immobilization method of MIL-101(Cr) positively affected the adsorption of polysulfides, while the bimetallic composite Cr2O3/MnOx formed by the doping of sulfur-loving Mn2+ into the porous MOF produced a good catalytic effect during LSB charging. This research provides a novel approach for preparing efficient sulfur-containing materials for LSBs.

| S-EPMC10223926 | biostudies-literature

Constructing free standing metal organic framework MIL-53 membrane based on anodized aluminum oxide precursor.

Project description:Metal organic framework (MOF) materials have attracted great attention due to their well-ordered and controllable pores possessing of prominent potentials for gas molecule sorption and separation performances. Organizing the MOF crystals to a continuous membrane with a certain scale will better exhibit their prominent potentials. Reports in recent years concentrate on well grown MOF membranes on specific substrates. Free standing MOF membranes could have more important applications since they are independent from the substrates. However, the method to prepare such a membrane has been a great challenge because good mechanical properties and stabilities are highly required. Here, we demonstrate a novel and facile technique for preparing the free standing membrane with a size as large as centimeter scale. The substrate we use proved itself not only a good skeleton but also an excellent precursor to fulfill the reaction. This kind of membrane owns a strong mechanical strength, based on the fact that it is much thinner than the composite membranes grown on substrates and it could exhibit good property of gas separation.

| S-EPMC4018608 | biostudies-literature

Pressure-induced postsynthetic cluster anion substitution in a MIL-53 topology scandium metal-organic framework.

Project description:Postsynthetic modification of metal-organic frameworks (MOFs) has proven to be a hugely powerful tool to tune physical properties and introduce functionality, by exploiting reactive sites on both the MOF linkers and their inorganic secondary building units (SBUs), and so has facilitated a wide range of applications. Studies into the reactivity of MOF SBUs have focussed solely on removal of neutral coordinating solvents, or direct exchange of linkers such as carboxylates, despite the prevalence of ancillary charge-balancing oxide and hydroxide ligands found in many SBUs. Herein, we show that the μ2-OH ligands in the MIL-53 topology Sc MOF, GUF-1, are labile, and can be substituted for μ2-OCH3 units through reaction with pore-bound methanol molecules in a very rare example of pressure-induced postsynthetic modification. Using comprehensive solid-state NMR spectroscopic analysis, we show an order of magnitude increase in this cluster anion substitution process after exposing bulk samples suspended in methanol to a pressure of 0.8 GPa in a large volume press. Additionally, single crystals compressed in diamond anvil cells with methanol as the pressure-transmitting medium have enabled full structural characterisation of the process across a range of pressures, leading to a quantitative single-crystal to single-crystal conversion at 4.98 GPa. This unexpected SBU reactivity - in this case chemisorption of methanol - has implications across a range of MOF chemistry, from activation of small molecules for heterogeneous catalysis to chemical stability, and we expect cluster anion substitution to be developed into a highly convenient novel method for modifying the internal pore surface and chemistry of a range of porous materials.

| S-EPMC10355111 | biostudies-literature

MIL-53-based homochiral metal-organic framework as a stationary phase for open-tubular capillary electrochromatography.

Project description:Homochiral metal-organic frameworks (MOFs) have attracted considerable attention in many fields of research, such as chiral catalysis and chiral chromatography. However, only few homochiral MOFs can be effectively used in capillary electrochromatography (CEC) and their performances are far from adequate. In this study, we successfully synthesized achiral nanocrystalline MIL-53. A facile post-synthetic modification strategy was then implemented to functionalize the product, yielding a homochiral MOF: l-His-NH-MIL-53. This MOF was then employed as a chiral coating in open-tubular CEC mode (OT-CEC), and, as such, it exhibited high enantioselectivities for several racemic drugs. The homochiral MOF and the fabricated capillary coating were systematically characterized using transmission electron microscopy, scanning electron microscopy (with energy-dispersive X-ray spectrometry), Fourier-transform infrared spectroscopy, X-ray diffractometry, thermogravimetric analysis, circular dichroism spectroscopy, Brunauer-Emmett-Teller surface area measurements, and X-ray photoelectron spectroscopy. This study is expected to provide a new strategy for the design and establishment of MOF-based chiral OT-CEC systems.

| S-EPMC9257441 | biostudies-literature

Nanoengineered Ultralight and Robust All-Metal Cathode for High-Capacity, Stable Lithium-Oxygen Batteries.

Project description:The successful development of Li-O2 battery technology depends on resolving the issue of cathode corrosion by the discharge product (Li2O2) and/or by the intermediates (LiO2) generated during cell cycling. As an important step toward this goal, we report for the first time the nanoporous Ni with a nanoengineered AuNi alloy surface directly attached to Ni foam as a new all-metal cathode system. Compared with other noncarbonaceous cathodes, the Li-O2 cell with an all-metal cathode is capable of operation with ultrahigh specific capacity (22,551 mAh g-1 at a current density of 1.0 A g-1) and long-term life (286 cycles). Furthermore, compared with the popularly used carbon cathode, the new all-metal cathode is advantageous because it does not show measurable reactivity toward Li2O2 and/or LiO2. As a result, extensive cyclability (40 cycles) with 87.7% Li2O2 formation and decomposition was obtained. These superior properties are explained by the enhanced solvation-mediated formation of the discharge products as well as the tailored properties of the all-metal cathode, including intrinsic chemical stability, high specific surface area, highly porous structure, high conductivity, and superior mechanical stability.

| S-EPMC5492421 | biostudies-literature

Synthesis and Properties of a Compositional Series of MIL-53(Al) Metal-Organic Framework Crystal-Glass Composites.

Project description:Metal-organic framework crystal-glass composites (MOF-CGCs) are materials in which a crystalline MOF is dispersed within a MOF glass. In this work, we explore the room-temperature stabilization of the open-pore form of MIL-53(Al), usually observed at high temperature, which occurs upon encapsulation within a ZIF-62(Zn) MOF glass matrix. A series of MOF-CGCs containing different loadings of MIL-53(Al) were synthesized and characterized using X-ray diffraction and nuclear magnetic resonance spectroscopy. An upper limit of MIL-53(Al) that can be stabilized in the composite was determined for the first time. The nanostructure of the composites was probed using pair distribution function analysis and scanning transmission electron microscopy. Notably, the distribution and integrity of the crystalline component in a sample series were determined, and these findings were related to the MOF-CGC gas adsorption capacity in order to identify the optimal loading necessary for maximum CO2 sorption capacity.

| S-EPMC7007233 | biostudies-literature

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