Browse
Submit Data
Databases
API
Help

Dataset Information

23 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Exploiting parameter space in MOFs: a 20-fold enhancement of phosphate-ester hydrolysis with UiO-66-NH2.

ABSTRACT: The hydrolysis of nerve agents is of primary concern due to the severe toxicity of these agents. Using a MOF-based catalyst (UiO-66), we have previously demonstrated that the hydrolysis can occur with relatively fast half-lives of 50 minutes. However, these rates are still prohibitively slow to be efficiently utilized for some practical applications (e.g., decontamination wipes used to clean exposed clothing/skin/vehicles). We thus turned our attention to derivatives of UiO-66 in order to probe the importance of functional groups on the hydrolysis rate. Three UiO-66 derivatives were explored; UiO-66-NO2 and UiO-66-(OH)2 showed little to no change in hydrolysis rate. However, UiO-66-NH2 showed a 20 fold increase in hydrolysis rate over the parent UiO-66 MOF. Half-lives of 1 minute were observed with this MOF. In order to probe the role of the amino moiety, we turned our attention to UiO-67, UiO-67-NMe2 and UiO-67-NH2. In these MOFs, the amino moiety is in close proximity to the zirconium node. We observed that UiO-67-NH2 is a faster catalyst than UiO-67 and UiO-67-NMe2. We conclude that the role of the amino moiety is to act as a proton-transfer agent during the catalytic cycle and not to hydrogen bond or to form a phosphorane intermediate.

SUBMITTER: Katz MJ

PROVIDER: S-EPMC5645779 | biostudies-literature | 2015 Apr

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

PANI@UiO-66 and PANI@UiO-66-NH2 Polymer-MOF Hybrid Composites as Tunable Semiconducting Materials.

Project description:This investigation explores optimum synthetic conditions for novel polymer-metal organic framework hybrid composites composed of Zr-terephthalate-based MOF UiO-66 and conductive polyaniline (PANI) nanofibers in an effort to optimize conductivity while minimizing MOF structural deformation. Successful syntheses of self-assembled PANI nanofibers in PANI@UiO-66 and PANI@UiO-66-NH2 composites were confirmed using scanning electron microscopy, infrared spectroscopy, and powder X-ray diffraction. The polymer-MOF composites show different bonding synergies to the PANI nanofibers depending on the organic linker used. Electronic properties of the post-synthetically modified PANI@UiO-66 and PANI@UiO-66-NH2 were investigated using UV-vis diffuse reflectance spectroscopy. Sheet resistivity of the self-assembled polymer-MOF composites was determined under an inert atmosphere at room temperature using four-point probe measurements to confirm tunable semiconductivity ranging from 40 to 2 mS/sq. Furthermore, the effects of aniline oxidation on the crystallinity and coordination of UiO-66 and UiO-66-NH2 were determined through analysis of these results.

| S-EPMC7114136 | biostudies-literature

UiO-66-NH2 and Zeolite-Templated Carbon Composites for the Degradation and Adsorption of Nerve Agents.

Project description:Composites of metal-organic frameworks and carbon materials have been suggested to be effective materials for the decomposition of chemical warfare agents. In this study, we synthesized UiO-66-NH2/zeolite-templated carbon (ZTC) composites for the adsorption and decomposition of the nerve agents sarin and soman. UiO-66-NH2/ZTC composites with good dispersion were prepared via a solvothermal method. Characterization studies showed that the composites had higher specific surface areas than pristine UiO-66-NH2, with broad pore size distributions centered at 1-2 nm. Owing to their porous nature, the UiO-66-NH2/ZTC composites could adsorb more water at 80% relative humidity. Among the UiO-66-NH2/ZTC composites, U0.8Z0.2 showed the best degradation performance. Characterization and gas adsorption studies revealed that beta-ZTC in U0.8Z0.2 provided additional adsorption and degradation sites for nerve agents. Among the investigated materials, including the pristine materials, U0.8Z0.2 also exhibited the best protection performance against the nerve agents. These results demonstrate that U0.8Z0.2 has the optimal composition for exploiting the degradation performance of pristine UiO-66-NH2 and the adsorption performance of pristine beta-ZTC.

| S-EPMC8270328 | biostudies-literature

UiO‐66 and hcp UiO‐66 Catalysts Synthesized from Ionic Liquids as Linker Precursors

Project description:Abstract Using ionic liquids (ILs) as linker precursors, the well‐known metal‐organic framework (MOF) UiO‐66 (Universitetet i Oslo) and the recently reported MOF hcp UiO‐66 (hexagonal closed packed) have been successfully synthesized and characterized. The advantage of the applied novel synthesis approach is an economically and environmentally benign work‐up procedure, due to the better solubility of the IL. Additionally, the reactivity of the terephthalate anions is increased compared to terephthalic acid, resulting in faster MOF formation with an increased amount of defects in the MOF structure. In order to explore to the influence of defects on the catalytic performance, the cyclisation of citronellal to isopulegol was employed as test reaction. The activity of hcp UiO‐66 and fcc UiO‐66 (face centered cubic) is improved compared to other MOF or zeolite based catalysts, while the selectivity is similar. The use of ionic liquids as linker precursor for the synthesis of the metal‐organic frameworks hcp and fcc UiO‐66 results in faster crystallization thereby reducing synthesis time and energy consumed. Furthermore, the catalytic activity of the MOFs in the cyclization of citronellal to isopulegol is increased due to defects within the frameworks while the selectivity is not affected.

| S-EPMC7874251 | biostudies-literature

Liquid-Phase Quasi-Epitaxial Growth of Highly Stable, Monolithic UiO-66-NH2 MOF thin Films on Solid Substrates.

Project description:High quality, monolithic UiO-66-NH2 thin films on diverse solid substrates have been prepared via a low temperature liquid phase epitaxy method. The achievement of continuous films with low defect densities and great stability against high temperatures and hot water is proven, clearly outperforming other reported types of MOF thin films.

| S-EPMC7197087 | biostudies-literature

Preparation of a g-C3N4/UiO-66-NH2/CdS Photocatalyst with Enhanced Visible Light Photocatalytic Activity for Tetracycline Degradation.

Project description:A combination of calcination and hydrothermal processing was used to prepare a g-C3N4/UiO-66-NH2/CdS photocatalyst, and the degradation of tetracycline (TC) over this material was assessed. The photocatalytic performance of this nanocomposite was approximately 4.4 and 2.3 times those of CdS and g-C3N4, respectively, and was found to be affected by the CdS loading amount, the pH of the reaction solution and the initial TC concentration. This catalyst also exhibited stable performance over four consecutive reaction cycles. The highly enhanced photoactivity of the g-C3N4/UiO-66-NH2/CdS is attributed to the introduction of CdS, which widens the range over which the material absorbs visible light and inhibits the recombination of electron-hole pairs. The results of this study suggest further applications for this material in the treatment of contaminated wastewater powered by solar energy.

| S-EPMC7558207 | biostudies-literature

Dynamic acidity in defective UiO-66.

Project description:The metal-organic framework (MOF) material UiO-66 has emerged as one of the most promising MOF materials due to its thermal and chemical stability and its potential for catalytic applications. Typically, as-synthesised UiO-66 has a relatively high concentration of missing linker defects. The presence of these defects has been correlated with catalytic activity but characterisation of defect structure has proved elusive. We refine a recent experimental determination of defect structure using static and dynamic first principles approaches, which reveals a dynamic and labile acid centre that could be tailored for functional applications in catalysis.

| S-EPMC6016445 | biostudies-literature

Synthesis and application of [Zr-UiO-66-PDC-SO<sub>3</sub>H]Cl MOFs to the preparation of dicyanomethylene pyridines via chemical and electrochemical methods.

Project description:A metal-organic framework (MOF) with sulfonic acid tags as a novel mesoporous catalyst was synthesized. The precursor of Zr-UiO-66-PDC was synthesized both via chemical and electrochemical methods. Then, zirconium-based mesoporous metal-organic framework [Zr-UiO-66-PDC-SO3H]Cl was prepared by reaction of Zr-UiO-66-PDC and SO3HCl. The structure of [Zr-UiO-66-PDC-SO3H]Cl was confirmed by FT-IR, PXRD, FE-SEM, TEM, BET, EDX, and Mapping analysis. This mesoporous [Zr-UiO-66-PDC-SO3H]Cl was successfully applied for the synthesis of dicyanomethylene pyridine derivatives via condensation of various aldehyde, 2-aminoprop-1-ene-1,1,3-tricarbonitrile and malononitrile. At the electrochemical section, a green electrochemical method has successfully employed for rapid synthesis of the zirconium-based mesoporous metal-organic framework UiO-66-PDC at room temperature and atmospheric pressure. The synthesized UiO-66-PDC has a uniform cauliflower-like structure with a 13.5 nm mean pore diameter and 1081.6 m2 g-1 surface area. The described catalyst [Zr-UiO-66-PDC-SO3H]Cl was also employed for the convergent paired electrochemical synthesis of dihydropyridine derivatives as an environmentally friendly technique under constant current at 1.0 mA cm-2 in an undivided cell. The proposed method proceeds with moderate to good yields for the model via a cooperative vinylogous anomeric based oxidation.

| S-EPMC8377142 | biostudies-literature

The Remarkable Amphoteric Nature of Defective UiO-66 in Catalytic Reactions.

Project description:One of the major requirements in solid acid and base catalyzed reactions is that the reactants, intermediates or activated complexes cooperate with several functions of catalyst support. In this work the remarkable bifunctional behavior of the defective UiO-66(Zr) metal organic framework is shown for acid-base pair catalysis. The active site relies on the presence of coordinatively unsaturated zirconium sites, which may be tuned by removing framework linkers and by removal of water from the inorganic bricks using a dehydration treatment. To elucidate the amphoteric nature of defective UiO-66, the Oppenauer oxidation of primary alcohols has been theoretically investigated using density functional theory (DFT) and the periodic approach. The presence of acid and basic centers within molecular distances is shown to be crucial for determining the catalytic activity of the material. Hydrated and dehydrated bricks have a distinct influence on the acidity and basicity of the active sites. In any case both functions need to cooperate in a concerted way to enable the chemical transformation. Experimental results on UiO-66 materials of different defectivity support the theoretical observations made in this work.

| S-EPMC5499726 | biostudies-literature

Evidence for a chemical clock in oscillatory formation of UiO-66.

Project description:Chemical clocks are often used as exciting classroom experiments, where an induction time is followed by rapidly changing colours that expose oscillating concentration patterns. This type of reaction belongs to a class of nonlinear chemical kinetics also linked to chaos, wave propagation and Turing patterns. Despite its vastness in occurrence and applicability, the clock reaction is only well understood for liquid-state processes. Here we report a chemical clock reaction, in which a solidifying entity, metal-organic framework UiO-66, displays oscillations in crystal dimension and number, as shown by X-ray scattering. In rationalizing this result, we introduce a computational approach, the metal-organic molecular orbital methodology, to pinpoint interaction between the tectonic building blocks that construct the metal-organic framework material. In this way, we show that hydrochloric acid plays the role of autocatalyst, bridging separate processes of condensation and crystallization.

| S-EPMC4906383 | biostudies-literature

Missing Linkers: An Alternative Pathway to UiO-66 Electronic Structure Engineering.

Project description:UiO-66 is a promising metal-organic framework for photocatalytic applications. However, the ligand-to-metal charge transfer of an excited electron is inefficient in the pristine material. Herein, we assess the influence of missing linker defects on the electronic structure of UiO-66 and discuss their ability to improve ligand-to-metal charge transfer. Using a new defect classification system, which is transparent and easily extendable, we identify the most promising photocatalysts by considering both relative stability and electronic structure. We find that the properties of UiO-66 defect structures largely depend on the coordination of the constituent nodes and that the nodes with the strongest local distortions alter the electronic structure most. Defects hence provide an alternative pathway to tune UiO-66 for photocatalytic purposes, besides linker modification and node metal substitution. In addition, the decomposition of MOF properties into node- and linker-based behavior is more generally valid, so we propose orthogonal electronic structure tuning as a paradigm in MOF design.

| S-EPMC5390508 | 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