One-dimensional Metal-organic Framework Research Articles

A solvent- and pH-stable NiII-based metal-organic framework with benzothiadiazole derivative for proton conduction

A one-dimensional metal–organic framework (MOF) with the formula of {[Ni(BIBT)(pydc)(H2O)2]·H2O}n (JXUST-26, BIBT = 4,7-bis(1H-imidazole-1-yl)-2,1,3-benzothiadiazole, H2pydc = 3,5-pyridinedicarboxylic acid) has been successfully synthesized under solvothermal condition, which crystallizes in the monoclinic C2/c space group. It is noteworthy that JXUST-26 exhibits good solvents and pH stabilities as well as relatively good thermal stability. The proton conductivity increases with increasing temperature, and reaches 1.65 × 10−8 S·cm−1 at 30 °C and 3.24 × 10−7 S·cm−1 at 80 °C under 98% relative humidity, respectively. In the low temperature range of 303–353 K, the activating energy (Ea) is 0.51 eV, which belongs to the Vehicle mechanism.

An all-embracing analytical method comprising modified QuEChERS-dispersive micro-solid-phase extraction-dispersive liquid-liquid microextraction using FeGA MOF for the extraction and preconcentration of pesticides simultaneously from juice and flesh of watermelon.

For the first time, a comprehensive analytical method based on a one-dimensional metal-organic framework comprising "quick, easy, cheap, effective, rugged, and safe-dispersive micro solid phase extraction-dispersive liquid-liquid microextraction" was introduced in this research. Moreover, the first-ever attempt was accomplished to apply the iron-gallic acid metal-organic framework in analytical method development. The goal of the research was to analyze the pesticide content of watermelon comprehensively in its flesh and juice. Based on this, comprehensive and reliable food safety monitoring can be done. Initially, pesticides of the watermelon flesh were extracted using an mL volume of acetonitrile by vortexing. At the same time, the pesticides of watermelon juice were extracted from the juice matrix onto the sorbent particles facilitated by vortexing. The obtained acetonitrile phase was also used to desorb the analytes from the sorbent surface by vortexing. As a result, the pesticide content of both juice and flesh was extracted into the acetonitrile. The pesticide-enriched acetonitrile was then used as the disperser solvent by being merged with µL level of 1,2-dibromoethane and injection into deionized water. A cloudy solution was created as the result. Centrifugation triggered extractant at the bottom of the conical glass test tube and an aliquot of it was injected into a gas chromatograph equipped with a flame ionization detector. High enrichment factors (210-400), appreciable extraction recoveries (42-80%), wide linear ranges (3.20-1000µgkg-1), relative standard deviations in the ranges of 3.6-4.4% for intra- (n = 6) and 4.4-5.3% for inter-day (n = 3) precisions, and low limits of detection (0.43-0.97µgkg-1), and quantification (1.42-3.20µgkg-1) were obtained by the application of the developed method.

Control of the pore chemistry in metal-organic frameworks for efficient adsorption of benzene and separation of benzene/cyclohexane

Control of the pore chemistry in metal-organic frameworks for efficient adsorption of benzene and separation of benzene/cyclohexane

Calculation of the number of conduction channels in a single-electron reservoir network on metal-organic framework polymers

Single-particle energy spectra of one-dimensional metal-organic framework chain’s fragments were obtained with the density functional theory method. An effective resistance of an organic part of the polymer, coulomb energy and effective capacitance of a charge center were calculated. The number of conductive channels in an experimentally studied reservoir network based on the observed polymer chains was estimated.

Curated Collection of More than 20,000 Experimentally Reported One-Dimensional Metal-Organic Frameworks.

A collection of more than 20,000 experimentally derived crystal structures for metal-organic frameworks (MOFs) that do not have two- or three-dimensional covalently bonded networks has been developed from the materials available at the Cambridge Crystallographic Data Centre. Of these 20,000 1D MOFs, more than 12,000 structures have been verified to be solvent-free and in exact agreement with the stoichiometry of the synthesized materials. More than 10% of the complete data set comprise materials including two or more distinct metals. The band gaps of more than 12,000 1D MOFs have been computed at the density functional theory-generalized gradient approximation level, finding more than 2000 materials that have a zero band gap. Molecular simulations of CH4 adsorption in a small number of 1D MOFs indicated that adsorbate-induced deformation plays a significant role in determining adsorption isotherms in these materials. As a result, methods that have been used previously for high-throughput predictions of molecular adsorption in 3D MOFs are not suitable for 1D MOFs.

Nanoporous carbon nanowires derived from one-dimensional metal-organic framework core-shell hybrids for enhanced electrochemical energy storage

One-dimensional core-shell metal-organic framework (MOF) hybrids is expected to combine the merits of one-dimensional structure and core-shell configuration, which shows superiority to the three-dimensional counterparts and the single core or shell MOFs. However, the construction of one-dimensional MOF core-shell hybrids still remains challenging to date. In this manuscript, one-dimensional MOF core-shell heterogeneous nanowires are successfully fabricated via a solvent-assisted transformation approach. After a simple carbonization treatment, nanoporous carbon nanowires derived from the prepared MOF core-shell hybrids can be obtained, in which a nitrogen-doped carbon shell is tightly decorated on a graphite carbon core. Due to such an unique nanostructure, the core-shell MOF-derived nanoporous carbon nanowires exhibit enhanced specific capacity, rate and cycling performance for electrochemical Li+ storage in comparison to the counterparts derived from single core and shell MOFs. The present study clearly reveals the importance of MOF structural engineering.

Synthesis of Nickel Fumarate and Its Electrochemical Properties for Li-Ion Batteries

Metal–organic frameworks (MOFs) have found a potential application in various domains such as gas storage/separation, drug delivery, catalysis, etc. Recently, they have found considerable attention for energy storage applications such as Li- and Na-ion batteries. However, the development of MOFs is plagued by their limited energy density that arises from high molecular weight and low volumetric density. The choice of ligand plays a crucial role in determining the performance of the MOFs. Here, we report a nickel-based one-dimensional metal-organic framework, NiC4H2O4, built from bidentate fumarate ligands for anode application in Li-ion batteries. The material was obtained by a simple chimie douce precipitation method using nickel acetate and fumaric acid. Moreover, a composite material of the MOF with reduced graphene oxide (rGO) was prepared to enhance the lithium storage performance as the rGO can enhance the electronic conductivity. Electrochemical lithium storage in the framework and the effect of rGO on the performance have been investigated by cyclic voltammetry, galvanostatic charge–discharge measurements, and EIS studies. The pristine nickel formate encounters serious capacity fading while the rGO composite offers good cycling stability with high reversible capacities of over 800 mAh g−1.

First-Principles Evaluation of One-Dimensional Metal-Organic Frameworks for Electrocatalytic C-H Activation of Natural Gas.

To replace the oxygen evolution reaction with thermodynamically more favorable and economically more profitable methane and ethane (the major components of natural gas) electrochemical partial oxidation, we employed constant electrode potential density functional theory calculations to screen 20 one-dimensional metal-organic frameworks containing heteroatom-substituted benzene as electrocatalysts. By computing the Pourbaix diagrams, O-H binding energies, and C-H activation barriers, we determined that although none of these catalysts were able to activate methane, one was able to hydroxylate ethane to ethanol with facile kinetics, making it a promising electrocatalyst for natural gas oxidation.

Preparation, crystal structures, properties, and time-dependent density functional theory of two cobalt complexes with 3-hydroxy-2-methyl-quinoline-4-carboxylate

One organic compound [HMCA]2 (1) and two novel cobalt complexes [Co(MCA)(bipy)(H2O)]·(H2O) (2), [Co2(MCA)2(Phen)3]·3(H2O) (3) are synthesized by a solvothermal approach and are structurally determined by single-crystal X-ray diffraction. Compound 1 exhibits a two-dimensional structure by hydrogen bond and π. . .π stacking interaction. The complexes exhibit a three-dimensional and one-dimensional metal-organic framework. Solid-state photoluminescence spectrums reveal that they show blue emission bands at 449 nm, and theoretical calculation results of time-dependent density functional theory show that all belong to ligand-to-ligand charge transfer. Solid-state diffuse reflectance spectrums reveal the presence of a narrow optical band gap of 1.72 and 1.60 eV in the complexes 2 and 3, respectively.

High 3D Proton Conductivity of a 2D Zn(II) Metal–Organic Framework Synthesized via Water-Assisted Single-Crystal-to-Single-Crystal Phase Transformation

In the present work, a one-dimensional metal-organic framework, {[Zn3(TBIB)2(Cl)6]11H2O}n (1), has been synthesized under high temperature and acidic conditions by utilizing the tripodal ligand 1,...

Metal-organic frameworks based on 1,5-bis(3,5-dimethylpyrazol-1-yl)-3-selenapentane: synthesis, structure, and properties

Four new metal-organic frameworks were synthesized based on the N-donor ligand 1,5-bis(3,5-dimethylpyrazol-1-yl)-3-selenapentane (L) novel in this field of chemistry: three one-dimensional metal-organic frameworks based on silver(I) cations, [Ag3(L)2(NO3)2]-NO3·MeOH (1), [Ag(L)]NO3 (2), and [Ag(L)(H2O)]NO3 (3), and one three-dimensional metal-organic framework [Zn3(bdc)3(L)]·0.5 MeOH (4, H2bdc is 1,4-benzenedicarboxylic acid). Compounds 1 and 4 contain trinuclear units. In compound 1, these units are linked via the ligand L to form polymer chains. In compound 4, the ligand L bridges polymer layers, which are composed of carboxylate units {Zn3(bdc)6}, to form a three-dimensional framework. Compounds 2 and 3 are composed of mononuclear units, which are connected via the ligand L to form polymer chains. Luminescence of compound 3 was found to be due to intraligand transitions.

Template-Assisted Fabrication of ZnO/Co3O4 One-Dimensional Metal–Organic Framework Array Decorated with Amorphous Iron Oxide/Hydroxide Nanoparticles as an Efficient Electrocatalyst for the Oxygen Evolution Reaction

The construction of new electrocatalysts for effective and low-cost water electrolysis continues to be an important conceptual barrier for clean renewable energy technologies. Herein, we fabricate ...

Preparation and Electrochemical Studies of Metal Fluorides for Lithium Batteries

Conventional positive (cathodes) electrode materials for lithium batteries, use mixed-conducting lithium containing transition metal oxides, metal phosphates etc. which are able to store both lithium and electrons by changing their oxidation state. In this presentation, we discuss the facile synthesis of materials suitable for alternative electrode concepts including Transition metal fluorides MF2 (M=Fe, Mn, Zn) were obtained by reacting Fe, Mn, Zn-Metal salts with fumaric acid as a one-dimensional metal organic framework, and a polymer (PVDF) as Fluorine source, final products are obtained by heating at 600°C, 6h in Ar gas. The MOF were initially prepared by a simple chimie douce method. Incorporation of the MOF with a fluorinated polymer and the eventual decomposition lead to carbon coated metal fluoride nanoparticles of high surface area of >200 m2/g for FeF2. The obtained materials will be characterized in detail by X-ray diffraction, Scanning and Transmission electron microscope (SEM/TEM) are used to evaluate the structure and morphology, X-ray photoelectron spectroscopy are used understand structure, vibrational bands and oxidation state of the materials and BET surface area method. Electrochemical studies were carried out in the voltage, range 4 to 1.0 vs. Li, at current rate of 50 mA/g (0.1 C) using 1MLiPF6 (EC;DEC) as liquid electrolyte and tested with Li-metal as a counter and reference electrodes. The cyclic voltammetry at scan rate of 0.075 mV/sec at room temperature (24°C). Galvanostatic cycling of FeF2 demonstrates that the material exhibit stable and good reversible capacity of 580 mAh/g during the first cycle and slight capacity fading has been observed after 20 cycles. Further studies on rate performance is being carried up to 2.5 C rate. Whereas MnF2 and ZnF2 showed reversible capacity of 220 and 200 mAh/g and retained a capacity around 100 mAh/g after 20 cycles and showed lower capacity than FeF2. Discuss the structural, reaction mechanism of FeF2 during charge-discharge cycling by in situ/operando X-ray diffraction and electrochemical impedance spectroscopy studies discuss in detail.Keywords: Metal fluorides (MF2 M=Fe, Zn, Mn); Electrochemical properties; Insitu studies; Electrochemical impedance spectroscopy; energy storage

Bis(iminothiolato)-Based One-Dimensional Metal–Organic Framework: Robust Bipolar Magnetic Semiconductor with Reversal of Spin Polarization

On the basis of first-principle calculations, we have studied the electronic and magnetic properties of a series of one-dimensional metal–organic frameworks (MOFs), labeled as MIT. These are coordinative assembly of first-row transition metals (M = Cr, Mn, Fe, and Co) and bis(iminothiolato) ligand (IT). Our calculation reveals that these MOFs are direct band gap semiconductors; specially, MnIT and FeIT are bipolar magnetic semiconductors having a ferromagnetic ground state. The trans-diradical electronic configuration and strong orbital hybridization lead to a robust bipolar magnetic semiconductor property against substituent effect and influence of an external transverse electric field. However, reversible spin polarization is obtained by simply applying bias voltage. Thus, our study paves the way for applying these 1D MOFs as bipolar magnetic spintronics materials.

Molecular discovery of half-metallic one-dimensional metal-organic framework

The metal-organic framework (MOF) is a large family of nanomaterials with tunable structural and electronic properties. Discovering half-metallic MOF can broaden the selection pool of half-metals for specific applications in the areas of electronics and catalysis. In this study, seven one-dimensional first-row transition metal-dithiolene MOFs have been systematically investigated using the first-principles density functional theory method. Our theoretical outcomes reveal that the electrical conductivities of these MOFs are determined by the electronic configurations of the metal cations. They can change from a semiconductor to a half-metal and further to a metal as the atomic number increases. Among all MOFs we considered, Cr(III)/Mn(III)/Fe(III)/Co(III)-dithiolene MOFs are promising candidates for spintronic applications.

Revisiting Anisotropic Diffusion of Carbon Dioxide in the Metal–Organic Framework Zn2(dobpdc)

The diffusion of gases confined in nanoporous materials underpins membrane and adsorption-based gas separations, yet relatively few measurements of diffusion coefficients in the promising class of materials, metal–organic frameworks (MOFs), have been reported to date. Recently we reported self-diffusion coefficients for 13CO2 in the MOF Zn2(dobpdc) (dobpdc4– = 4,4′-dioxidobiphenyl-3,3′-dicarboxylate) which has one-dimensional channels with a diameter of approximately 2 nm [Forse, A. C.; J. Am. Chem. Soc. 2018, 140, 1663−1673]. By analyzing the evolution of the residual 13C chemical shift anisotropy line shape at different gradient strengths, we obtained self-diffusion coefficients both along (D∥) and between (D⊥) the one-dimensional MOF channels. The observation of nonzero D⊥ was unexpected based on the single crystal X-ray diffraction structure and flexible lattice molecular dynamics simulations, and we proposed that structural defects may be responsible for self-diffusion between the MOF channels. Here ...

Electrolyte Effect on Electrocatalytic Hydrogen Evolution Performance of One-Dimensional Cobalt–Dithiolene Metal–Organic Frameworks: A Theoretical Perspective

Discovering inexpensive and earth-abundant electrocatalysts to replace the scarce platinum group metal-based electrocatalysts holds the key for large-scale hydrogen fuel generation, which relies heavily on the theoretical understanding of the properties of candidate materials and their operating environment. The recent applications of the cobalt–dithiolene complex as promising electrocatalysts for the hydrogen evolution reaction have been broadened by forming low-dimensional metal–organic frameworks (MOFs) through polymerization. Using the Gibbs free energy of the adsorption of hydrogen atoms as a key descriptor, S atoms within one-dimensional MOFs are identified to be the preferred catalytic site for HERs. Our theoretical results further reveal that the activities of part S atoms can be improved by interacting with alkali metal cations from the electrolytes; specifically, the influence of cations on the performance is dependent on the electron affinity of cations. Our theoretical findings, therefore, demonstrate that the selection of electrolytes can be a promising approach to enhance the performance of electrocatalysts for HERs.

α-Ferrous oxalate dihydrate: an Fe-based one-dimensional metal organic framework with extraordinary photocatalytic and Fenton activities

An Fe(ii)-based metal organic framework, α-ferrous oxalate dihydrate (α-FOD), with remarkable n-type semiconductor characteristics has been successfully prepared for use as a bifunctional catalyst in both photocatalysis and Fenton oxidation.

Anisotropic self-diffusion of fluorinated poly(methacrylate) in metal–organic frameworks assessed with molecular dynamics simulation**Project supported by the National Natural Science Foundation of China (Grant No. 61575096).

Utilizing the periodically structured metal–organic framework (MOF) as the reaction vessel is a promising technique to achieve the aligned polymer molecular chains, where the diffusion procedure of the polymer monomer inside MOF is one of the key mechanisms. To investigate the diffusion mechanism of fluorinated polymer monomers in MOFs, in this paper the molecular dynamics simulations combined with the density functional theory and the Monte Carlo method are used and the all-atom models of TFMA (trifluoroethyl methacrylate) monomer and two types of MOFs, [Zn2(BDC)2(TED)]n and [Zn2(BPDC)2(TED)]n, are established. The diffusion behaviors of TFMA monomer in these two MOFs are simulated and the main influencing factors are analyzed. The obtained results are as follows. First, the electrostatic interactions between TFMA monomers and MOFs cause the monomers to concentrate in the MOF channel, which slows down the monomer diffusion. Second, the anisotropic shape of the one-dimensional MOF channel leads to different diffusion speeds of monomers in different directions. Third, MOF with a larger pore diameter due to a longer organic ligand, [Zn2(BPDC)2(TED)]n in this paper, facilitates the diffusion of monomers in the MOF channel. Finally, as the number of monomers increases, the self-diffusion coefficient is reduced by the steric effect.

One-dimensional metal-organic frameworks based on N-heterocyclic ligand and 5-Amino-isophthalic acid: Synthesis, structure, and photoluminescent properties

ABSTRACTOne complex [Mn(dnpt)(aic)]n [dnpt = 2-(4-nitrophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline, aic = 5-Amino-isophthalic acid] was obtained from hydrothermal reaction and was characterized by elemental analysis, IR, and single-crystal X-ray diffraction. The crystal structure shows that the manganese ion is coordinated with two nitrogen atoms of one dnpt molecule and four oxygen atoms from three aic molecules, forming a distorted octahedral coordination geometry. Each Mn(II) atom is linked by aic ligands with neighbor Mn(II) atoms, forming an infinite one-dimensional (1D) double-chain structure. The luminescent properties for the ligand and complex 1 are also discussed in detail (CCDC 1030059).