Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Precise control of pore hydrophilicity enabled by post-synthetic cation exchange in metal-organic frameworks.

ABSTRACT: The ability to control the relative humidity at which water uptake occurs in a given adsorbent is advantageous, making that material applicable to a variety of different applications. Here, we show that cation exchange in a metal-organic framework allows precise control over the humidity onset of the water uptake step. Controlled incorporation of cobalt in place of zinc produces open metal sites into the cubic triazolate framework MFU-4l, and thereby provides access to materials with uptake steps over a 30% relative humidity range. Notably, the MFU-4l framework has an extremely high water adsorption capacity of 1.05 g g^-1, amongst the highest known for porous materials. The total water capacity is independent of the cobalt loading, showing that cation exchange is a viable route to increase the hydrophilicity of metal-organic frameworks without sacrificing capacity.

SUBMITTER: Wright AM

PROVIDER: S-EPMC5941795 | biostudies-literature | 2018 Apr

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Precise control of pore hydrophilicity enabled by post-synthetic cation exchange in metal-organic frameworks.

Wright Ashley M AM Rieth Adam J AJ Yang Sungwoo S Wang Evelyn N EN Dincă Mircea M

Chemical science 20180321 15

The ability to control the relative humidity at which water uptake occurs in a given adsorbent is advantageous, making that material applicable to a variety of different applications. Here, we show that cation exchange in a metal-organic framework allows precise control over the humidity onset of the water uptake step. Controlled incorporation of cobalt in place of zinc produces open metal sites into the cubic triazolate framework MFU-4<i>l</i>, and thereby provides access to materials with upta ...[more]

PMID: 29780517

Similar Datasets

Vapor-phase linker exchange of metal-organic frameworks.

Project description:Metal-organic frameworks (MOFs) have been attracting intensive attention because of their commendable potential in many applications. Postsynthetic modification for redesigning chemical characteristics and pore structures can greatly improve performance and expand functionality of MOF materials. Here, we develop a versatile vapor-phase linker exchange (VPLE) methodology for MOF modification. Through solvent-free and environment-friendly VPLE processing, various linker analogs with functional groups but not for straightforward MOF crystallization are inserted into frameworks as daughter building blocks. Besides single exchange for preparing MOFs with dual linkers, VPLE can further be performed by multistage operations to obtain MOF materials with multiple linkers and functional groups. The halogen-incorporated ZIFs exhibit good porosity, tunable molecular affinity, and impressive CO2/N2 and CH4/N2 adsorption selectivities up to 31.1 and 10.8, respectively, which are two to six times higher than those of conventional adsorbents. Moreover, VPLE can substantially enhance the compatibility of MOFs and polymers.

| S-EPMC7195121 | biostudies-literature

Exchange controlled triplet fusion in metal-organic frameworks.

Project description:Triplet-fusion-based photon upconversion holds promise for a wide range of applications, from photovoltaics to bioimaging. The efficiency of triplet fusion, however, is fundamentally limited in conventional molecular and polymeric systems by its spin dependence. Here, we show that the inherent tailorability of metal-organic frameworks (MOFs), combined with their highly porous but ordered structure, minimizes intertriplet exchange coupling and engineers effective spin mixing between singlet and quintet triplet-triplet pair states. We demonstrate singlet-quintet coupling in a pyrene-based MOF, NU-1000. An anomalous magnetic field effect is observed from NU-1000 corresponding to an induced resonance between singlet and quintet states that yields an increased fusion rate at room temperature under a relatively low applied magnetic field of 0.14 T. Our results suggest that MOFs offer particular promise for engineering the spin dynamics of multiexcitonic processes and improving their upconversion performance.

| S-EPMC9622415 | biostudies-literature

Uniform distribution of post-synthetic linker exchange in metal-organic frameworks revealed by Rutherford backscattering spectrometry.

Project description:Rutherford backscattering spectrometry (RBS) has been used for the first time to study post-synthetic linker exchange (PSE) in metal-organic frameworks. RBS is a non-invasive method to quantify the amount of introduced linker, as well as providing a means for depth profiling in order to identify the preferred localization of the introduced linker. The exchange of benzenedicarboxylate (bdc) by similarly sized 2-iodobenzenedicarboxylate (I-bdc) proceeds considerably slower than migration of I-dbc through the UiO-66 crystal. Consequently, the I-bdc is found evenly distributed throughout the UiO-66 samples, even at very short PSE exposure times.

| S-EPMC5846729 | biostudies-literature

Precise Control of Molecular Self-Diffusion in Isoreticular and Multivariate Metal-Organic Frameworks.

Project description:Understanding the factors that affect self-diffusion in isoreticular and multivariate (MTV) MOFs is key to their application in drug delivery, separations, and heterogeneous catalysis. Here, we measure the apparent self-diffusion of solvents saturated within the pores of large single crystals of MOF-5, IRMOF-3 (amino-functionalized MOF-5), and 17 MTV-MOF-5/IRMOF-3 materials at various mole fractions. We find that the apparent self-diffusion coefficient of N,N-dimethylformamide (DMF) may be tuned linearly between the diffusion coefficients of MOF-5 and IRMOF-3 as a function of the linker mole fraction. We compare a series of solvents at saturation in MOF-5 and IRMOF-3 to elucidate the mechanism by which the linker amino groups tune molecular diffusion. The ratio of the self-diffusion coefficients for solvents in MOF-5 to those in IRMOF-3 is similar across all solvents tested, regardless of solvent polarity. We conclude that average pore aperture, not solvent-linker chemical interactions, is the primary factor responsible for the different diffusion dynamics upon introduction of an amino group to the linker.

| S-EPMC7004185 | biostudies-literature

A new post-synthetic polymerization strategy makes metal-organic frameworks more stable.

Project description:Metal-organic frameworks are of interest in a number of host-guest applications. However, their weak coordination bonding often leads to instability in aqueous environments, particularly at extreme pH, and hence, is a challenging topic in the field. In this work, a two-step, post-synthetic polymerization method is used to create a series of highly hydrophobic, stable MOF composites. The MOFs are first coated with thin layers of polydopamine from free-base dopamine under a mild oxygen atmosphere, which then undergoes a Michael addition to covalently graft hydrophobic molecules to the external MOF surface. This easy, mild post-synthetic modification is shown to significantly improve the stability of a number of structurally diverse MOFs including HKUST-1 (Cu), ZIF-67 (Co), ZIF-8 (Zn), UiO-66 (Zr), Cu-TDPAT (Cu), Mg-MOF-74 (Mg) and MIL-100 (Fe) in wet, caustic (acidic and basic) environments as determined by powder X-ray diffraction and surface area measurements.

| S-EPMC6498544 | biostudies-other

Symmetry-guided syntheses of mixed-linker Zr metal-organic frameworks with precise linker locations.

Project description:While the one-pot reaction of zirconium metal ions with a mixture of two dicarboxylate heterolinkers yielded a 12-c fcu Zr MOF with randomly distributed linkers, the symmetry-guided stepwise reaction produced the same MOF with both linkers precisely located in the framework. In the latter method, linear terephthalic acid (H2BDC) derivatives with mmm symmetry were inserted into the mmm-symmetry sites of the flexible Zr MOF with 8-c bcu topology (ZRN-bcu), which is composed of zigzag 2,6-naphthalenedicarboxylic acid with 2/m symmetry. Although the length of the symmetry-matching BDC2- derivatives was much shorter than the distance between the unlinked nearest-neighbor Zr clusters in ZRN-bcu, induced fitting of the derivatives into the framework was possible, resulting in well-defined locations for the two different dicarboxylate linkers. Thus, controlled synthesis of MOFs with the desired topology and functionality can be achieved using a symmetry-guided approach.

| S-EPMC6568281 | biostudies-literature

Capture and Separation of SO<sub>2</sub> Traces in Metal-Organic Frameworks via Pre-Synthetic Pore Environment Tailoring by Methyl Groups.

Project description:Herein, we report a pre-synthetic pore environment design strategy to achieve stable methyl-functionalized metal-organic frameworks (MOFs) for preferential SO2 binding and thus enhanced low (partial) pressure SO2 adsorption and SO2 /CO2 separation. The enhanced sorption performance is for the first time attributed to an optimal pore size by increasing methyl group densities at the benzenedicarboxylate linker in [Ni2 (BDC-X)2 DABCO] (BDC-X=mono-, di-, and tetramethyl-1,4-benzenedicarboxylate/terephthalate; DABCO=1,4-diazabicyclo[2,2,2]octane). Monte Carlo simulations and first-principles density functional theory (DFT) calculations demonstrate the key role of methyl groups within the pore surface on the preferential SO2 affinity over the parent MOF. The SO2 separation potential by methyl-functionalized MOFs has been validated by gas sorption isotherms, ideal adsorbed solution theory calculations, simulated and experimental breakthrough curves, and DFT calculations.

| S-EPMC8457122 | biostudies-literature

Visualizing defects and pore connectivity within metal-organic frameworks by X-ray transmission tomography.

Project description:Metal-Organic Frameworks (MOFs) have the potential to change the landscape of molecular separations in chemical processes owing to their ability of selectively binding molecules. Their molecular sorting properties generally rely on the micro- and meso-pore structure, as well as on the presence of coordinatively unsaturated sites that interact with the different chemical species present in the feed. In this work, we show a first-of-its-kind tomographic imaging of the crystal morphology of a metal-organic framework by means of transmission X-ray microscopy (TXM), including a detailed data reconstruction and processing approach. Corroboration with Focused Ion Beam-Scanning Electron Microscopy (FIB-SEM) images shows the potential of this strategy for further (non-destructively) assessing the inner architecture of MOF crystals. By doing this, we have unraveled the presence of large voids in the internal structure of a MIL-47(V) crystal, which are typically thought of as rather homogeneous lattices. This challenges the established opinion that hydrothermal syntheses yield relatively defect-free material and sheds further light on the internal morphology of crystals.

| S-EPMC8221180 | biostudies-literature

Effect of pore size and shape on the thermal conductivity of metal-organic frameworks.

Project description:We investigate the effect of pore size and shape on the thermal conductivity of a series of idealized metal-organic frameworks (MOFs) containing adsorbed gas using molecular simulations. With no gas present, the thermal conductivity decreases with increasing pore size. In the presence of adsorbed gas, MOFs with smaller pores experience reduced thermal conductivity due to phonon scattering introduced by gas-crystal interactions. In contrast, for larger pores (>1.7 nm), the adsorbed gas does not significantly affect thermal conductivity. This difference is due to the decreased probability of gas-crystal collisions in larger pore structures. In contrast to MOFs with simple cubic pores, the thermal conductivity in structures with triangular and hexagonal pore channels exhibits significant anisotropy. For different pore geometries at the same atomic density, hexagonal channel MOFs have both the highest and lowest thermal conductivities, along and across the channel direction, respectively. In the triangular and hexagonal channeled structures, the presence of gas molecules has different effects on thermal conductivity along different crystallographic directions.

| S-EPMC5358541 | biostudies-literature

Adsorption in Pyrene-Based Metal-Organic Frameworks: The Role of Pore Structure and Topology.

Project description:Pore topology and chemistry play crucial roles in the adsorption characteristics of metal-organic frameworks (MOFs). To deepen our understanding of the interactions between MOFs and CO2 during this process, we systematically investigate the adsorption properties of a group of pyrene-based MOFs. These MOFs feature Zn(II) as the metal ion and employ a pyrene-based ligand, specifically 1,3,6,8-tetrakis(p-benzoic acid)pyrene (TBAPy). Including different additional ligands leads to frameworks with distinctive structural and chemical features. By comparing these structures, we could isolate the role that pore size, the presence of open-metal sites (OMS), metal-oxygen bridges, and framework charges play in the CO2 adsorption of these MOFs. Frameworks with constricted pore structures display a phenomenon known as the confinement effect, fostering stronger MOF-CO2 interactions and higher uptakes at low pressures. In contrast, entropic effects dominate at elevated pressures, and the MOF's pore volume becomes the driving factor. Through analysis of the CO2 uptakes of the benchmark materials ─some with narrower pores and others with larger pore volumes─it becomes evident that structures with narrower pores and high binding energies excel at low pressures. In contrast, those with larger volumes perform better at elevated pressures. Moreover, this research highlights that open-metal sites and inherent charges within the frameworks of ionic MOFs stand out as CO2-philic characteristics.

| S-EPMC11261566 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data