Metal–Organic Frameworks

Through comprehensive analysis of carboxylate-based metal-organic frameworks (MOFs), we present general evidence that challenges the common perception of MOF metal-linker bonds being static. Structural dynamics in MOFs, however, typically refers to the "breathing" behavior of cavities, where pores open and close in response to guest molecules, and to the transient binding of guest molecules, but dynamic bonding would explain important MOF phenomena in catalysis, postsynthetic exchange, negative thermal expansion, and crystal growth...

To exploit the full potential of metal-organic frameworks as solid adsorbents in water-adsorption applications, many challenges remain to be solved. A more fundamental insight into the properties of the host material and the influence that water exerts on them can be obtained by performing molecular simulations. In this work, the prototypical flexible MIL-53(Al) framework is modelled using advanced molecular dynamics simulations. For different water loadings, the presence of water is shown to affect the relative stability of MIL-53(Al), triggering a phase transition from the narrow-pore to the large-pore phase at the highest considered loading...

Many framework materials such as metal-organic frameworks (MOFs) or porous coordination polymers (PCPs) are synthesized as polycrystalline powders, which are too small for structure determination by single crystal X-ray diffraction (SCXRD). Here, we show that a three-dimensional (3D) electron diffraction method, namely continuous rotation electron diffraction (cRED), can be used for ab initio structure determination of such materials. As an example, we present the complete structural analysis of a biocomposite, denoted BSA@ZIF-CO3 -1, in which Bovine Serum Albumin (BSA) was encapsulated in a zeolitic imidazolate framework (ZIF)...

Alkaline earth metal ion organic frameworks (AEMOFs) represent a relatively underexplored subcategory of metal-organic frameworks (MOFs). In this contribution, we present the synthesis and structural study of the new MOFs 1-8 based on the alkaline earth ions Mg2+, Ca2+, Sr2+ and Ba2+ and the amino substituted bridging ligands 4-aminonaphthalene-2,6-dicarboxylate (ANDC2-) and 4,8-diaminonaphthalene-2,6-dicarboxylate (DANDC2-). Compounds 1, 5, 6, 7 and 8 constitute rare examples of three-dimensional MOFs which feature square planar M4 secondary building units (SBUs) surrounded by eight bridging ditopic ligands...

Efficient and selective hydrolysis of inert peptide bonds is of paramount importance. MOF-808, a metal-organic framework based on Zr6 nodes, can hydrolyze peptide bonds efficiently under biologically relevant conditions. However, the details of the catalyst structure and of the underlying catalytic reaction mechanism are challenging to establish. By means of DFT calculations we first investigate the speciation of the Zr6 nodes and identify the nature of ligands that bind to the Zr6O8H4-x core in aqueous conditions...

Unusual adsorption phenomena, such as breathing and negative gas adsorption (NGA), are rare and challenge our thermodynamic understanding of adsorption in deformable porous solids. In particular, NGA appears to break the rules of thermodynamics in these materials by exhibiting a spontaneous release of gas accompanying an increase in pressure. This anomaly relies on long-lived metastable states. A fundamental understanding of this process is desperately required for the discovery of new materials with this exotic property...

Metal-organic frameworks (MOFs) have sparked increasing interest in mimicking the structure and function of natural enzymes. However, their catalytic and therapeutic efficiency are unsatisfactory due to the relatively lower catalytic activity. Herein, inspired by nature, a MOF@COF nanozyme has been designed as a high-efficiency peroxidase mimic, with the metallic nodes of MOFs as active centres, the hierarchical nanocavities produced by the growth of covalent organic frameworks (COFs) as binding pockets to form tailored pore microenvironment around active sites for enriching and activating substrate molecules, to perform enhanced bacterial inhibition...

Background: Recent studies have validated and confirmed the great potential of nanoscale metal-organic framework (NMOF) in the biomedical field, especially in improving the efficiency of cancer diagnosis and therapy. However, most previous studies only utilized either the metal cluster or the organic ligand of the NMOF for cancer treatments and merely reported limited theranostic functions, which may not be optimized. As a highly designable and easily functionalized material, prospective rational design offers a powerful way to extract the maximum benefit from NMOF for cancer theranostic applications...

The separation of xylene isomers (para-, meta-, orth-) remains a great challenge in the petrochemical industry due to their similar molecular structure and physical properties. Porous materials with sensitive nanospace and selective binding sites for discriminating the subtle structural difference of isomers are urgently needed. Here, we demonstrate the adaptively molecular discrimination of xylene isomers by employing a NbOF5 2- -pillared metal-organic framework (NbOFFIVE-bpy-Ni, also referred to as ZU-61) with rotational anionic sites...

Refractive-index (RI)-based sensing is a major optical sensing modality that can be implemented in various spectral ranges. While it has been widely used for sensing of biochemical liquids, RI-based gas sensing, particularly small-molecule gases, is challenging due to the extremely small RI change induced by gas concentration variations. We propose a RI-based ultracompact fiber-optic differential gas sensor that employs metal-organic-framework (MOF)-based dual Fabry-Perot (FP) nanocavities. A MOF is used as the FP cavity material to enhance the sensitivity as well as the selectivity to particular gas molecules...

To alleviate the secondary risks of using metal-organic frameworks (MOFs) nanoparticles as adsorbent, a novel method of loading two MOFs (ZIF-8 or UiO66-NH2 ) on the carbon nanotube aerogels (MPCA) by in situ nucleation and growth of MOFs nanoparticles onto carbon nanotubes were developed. The prepared MOFs@MPCA aerogels were well characterized via SEM, TEM, EDS, FT-IR, XRD and XPS to reveal the microstructure and formation mechanism of MOF@MPCA. Besides, the hydrophilia, mechanical property and thermostability of MOF@MPCA were investigated...

Adsorptive separation is an appealing alternative technology to reduce the high energy and capital cost of the distillation separation of propylene/propane; however, it is very challenging to realize. A new flexible metal-organic framework (MOF) material [Zn2 (BDC-Cl)2 (Py2 TTz)] with a doubly interpenetrated pillared paddle wheel structure of pcu (primitive cubic) topology has been realized for this difficult separation for the first time. Through a judicious choice of linkers, the framework has small pore apertures that lead to much more propylene adsorption than propane...

In this study, we propose a versatile design for metal-organic framework cathodes with the aim of improving the reversibility of Li-O2 and Li-O2/CO2 batteries. The porous nanoarchitecture of Co3O4-incorporated carbon wrapped with carbon nanotubes is beneficial for facilitating the reversible electrochemical reactions with O2 and CO2, ensuring long-term cycling performance.

C2 separation is of great importance in the petrochemical industry. Traditionally, it is performed by distillation at cryogenic temperatures, which necessitates the consumption of a huge amount of energy to operate the refrigeration system in the production process. In this regard, it is imperative to seek alternative separation methods with high efficiency and low energy cost. Although of recent origin, metal-organic frameworks (MOFs) have already been extensively studied as advanced adsorbents in many applications, and significant progress has been made particularly in gas separation owing to their unprecedented porosity and tunable structures...

Metal organic framework (MOF)-encapsulated metal clusters have shown superior catalytic activity due to geometric and electronic properties of metal clusters, which are largely determined by adsorption sites and sizes and morphologies of encapsulated metal clusters. In the present work, anchoring sites, the stability, and the agglomeration probability of Ptn (n = 1-23) clusters over an MOF-808 framework structure were studied using density functional theory calculations and ab initio molecular dynamics simulation...

Although many metal-organic cages (MOCs) and a few hydrogen-bonded organic cages (HOCs) have been individually investigated, little is reported about the cooperative self-assembly of MOCs and HOCs. Herein, we first describe an unprecedented MOC&HOC co-crystal, which is composed of tetrahedral Ti4L6 (L = embonate) cages and in-situ generated [(NH3)4(TIPA)4] (TIPA = tris(4-(1H-1,2,4-triazol-1-yl)phenyl)amine) cages. Chiral transfer phenomenon is observed from enantiopure Ti4L6 cage to enantiopure [(NH3)4(TIPA)4] cage...

Adsorptive removal of dimethyl phthalate (DMP) in water combined with advanced oxidation processes (AOPs) has attracted interest. In this work, the adsorptive and catalytic properties of an Fe-based metal-organic framework (Fe-MOF-74) have been improved by molecular imprinting technique. The adsorption behaviors have been evaluated by the Freundlich and pseudo-second-order model. The results have shown that selective adsorption ability of the material for DMP was highly enhanced and chemisorption was dominating...

Metallothioneins (MTs) are a family of cysteine-rich metal-binding proteins that are important in the chelating and detoxification of toxic heavy metals. Until now, the short length and the low sequence complexity of MTs have hindered the inference of robust phylogenies, hampering the study of their evolution. To address this longstanding question, we applied an iterative BLAST search pipeline that allowed us to build a unique dataset of more than 300 MT sequences in insects. By combining phylogenetics and synteny analysis, we reconstructed the evolutionary history of MTs in insects...

Molecular motions taking place in the nanospace of metal-organic frameworks (MOFs) are an interesting research subject, although not yet fully investigated. In this work, we utilized in situ Raman spectroscopy in the ultralow-frequency region to investigate the libration motion (including the rotational motion of phenylene rings) of MOFs, in particular [Cu2(bdc)2(dabco)] (Cu-JAST-1), where bdc = 1,4-benzenedicarboxylate and dabco = 1,4-diazabicyclo[2.2.2]octane. The libration mode of Cu-JAST-1 was found to be significantly suppressed by the adsorption of various guest molecules, such as CO2, Ar, and N2...

The separation of C 2 H 2 /CO 2 is an essential but challenging process owing to their similar molecular sizes and physical properties. However, it is noteworthy that these two molecules usually exhibit different orientations in the pore channel. Herein, we report an adsorption site selective occupation strategy by taking advantage of differences in orientation to sieving the C 2 H 2 from CO 2 in a judiciously designed amine-functionalized metal-organic framework, termed as CPL-1-NH 2 . In this material, the incorporation of amino groups not only occupies the adsorption sites of CO 2 molecules and shields the interaction of uncoordinated oxygen atom and CO 2 molecules resulting in a negligible adsorption amount and a decrease in enthalpy of adsorption but also strengthened the binding affinity toward C 2 H 2 molecules...