Browse
Submit Data
Databases
API
Help

Dataset Information

41 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Vectorial Catalysis in Surface-Anchored Nanometer-Sized Metal-Organic Frameworks-Based Microfluidic Devices.

ABSTRACT: Vectorial catalysis-controlling multi-step reactions in a programmed sequence and by defined spatial localization in a microscale device-is an enticing goal in bio-inspired catalysis research. However, translating concepts from natural cascade biocatalysis into artificial hierarchical chemical systems remains a challenge. Herein, we demonstrate integration of two different surface-anchored nanometer-sized metal-organic frameworks (MOFs) in a microfluidic device for modelling vectorial catalysis. Catalyst immobilization at defined sections along the microchannel and a two-step cascade reaction was conducted with full conversion after 30 seconds and high turnover frequencies (TOF≈10⁵ h^-1 ).

SUBMITTER: Semrau AL

PROVIDER: S-EPMC9300199 | biostudies-literature | 2022 Feb

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Vectorial Catalysis in Surface-Anchored Nanometer-Sized Metal-Organic Frameworks-Based Microfluidic Devices.

Semrau Anna Lisa AL Stanley Philip M PM Huber Dominik D Schuster Michael M Albada Bauke B Zuilhof Han H Cokoja Mirza M Fischer Roland A RA

Angewandte Chemie (International ed. in English) 20211209 8

Vectorial catalysis-controlling multi-step reactions in a programmed sequence and by defined spatial localization in a microscale device-is an enticing goal in bio-inspired catalysis research. However, translating concepts from natural cascade biocatalysis into artificial hierarchical chemical systems remains a challenge. Herein, we demonstrate integration of two different surface-anchored nanometer-sized metal-organic frameworks (MOFs) in a microfluidic device for modelling vectorial catalysis. ...[more]

PMID: 34825766

Similar Datasets

In situ synthesis of sub-nanometer metal particles on hierarchically porous metal-organic frameworks via interfacial control for highly efficient catalysis.

Project description:In this work, we developed a strategy to in situ synthesize sub-nanometer metal particle/hierarchically mesoporous metal-organic framework (MOF) composites in emulsion. In this route, water droplets in the emulsion acted as both a solvent of the metal precursors and a template for the hierarchical mesopores of MOFs, and the surfactant was an emulsifier and a reductant for generating metal particles. Au/Zn-MOFs (MOFs formed by Zn2+ and methylimidazole), Ru/Zn-MOFs, Pd/Zn-MOFs, and Au/Cu-MOFs (MOFs formed by Cu2+ and methylimidazole) were prepared using this method, in which ultrafine metal particles (e.g. 0.8 nm) were immobilized uniformly on hierarchically mesoporous MOFs. Au/Zn-MOFs and Au/Cu-MOFs showed outstanding catalytic performances for the selective aerobic oxidation of cyclohexene to 2-cyclohexen-1-one in the absence of an initiator, and Ru/Zn-MOFs were very active and selective for the hydrogenation of diphenyl sulfoxide to diphenyl sulfide. In addition, the catalysts were also very stable in the reactions.

| S-EPMC5887229 | biostudies-literature

Polypyrrole decorated metal-organic frameworks for supercapacitor devices.

Project description:Due to their large specific surface areas and porosity, metal-organic frameworks (MOFs) have found many applications in catalysis, gas separation, and gas storage. However, their use as electronic components such as supercapacitors is stunted due to their poor electrical conductivity. We report a remedy for this by combining the MOF structure with polypyrrole (PPy), a well-known conductive polymer. Three MOFs are studied for modification to this end: CPO-27-Ni and CPO-27-Co (M2DOBDC, M = Ni2+, Co2+, DOBDC = 2,5-dihydroxy-1,4-benzenedicarboxylate) and HKUST-1 (Cu3(BTC)2, BTC = 1,3,5 benzenetricarboxylate). The gravimetric capacitance of pure MOFs is boosted several orders of magnitude after reinforcement of PPy (e.g., from 0.679 to 185 F g-1 for HKUST-1 and PPy-HKUST-1, respectively), and is much higher than reported for pure PPy. In total, these PPy-d-MOFs exhibit specific capacitances up to 354 F g-1, retaining 70% of this value even after 2500 cycles. Among them, the highest capacitance is found for PPy-CPO-27-Ni (354 F g-1), followed by PPy-CPO-27-Co (263 F g-1) and PPy-HKUST-1 (185 F g-1). The maximum operating potential for these electrodes is 0.5 V, which is restricted by the contact of MOF with aqueous electrolyte and with extremely low PPy content. As a solution, higher PPy loading and rational adjustment of particle size and porosity of both MOF and PPy are recommended so that the MOF/electrolyte interface is limited, leading to more robust electrode. The work completed here describes a highly promising approach to tackling the electrically insulating nature of MOFs, paving the way for their use in electrochemical energy storage devices.

| S-EPMC9054202 | biostudies-literature

Tunable chiral metal organic frameworks toward visible light-driven asymmetric catalysis.

Project description:A simple and effective strategy is developed to realize visible light-driven heterogeneous asymmetric catalysis. A chiral organic molecule, which only has very weak catalytic activity in asymmetric α-alkylation of aldehydes under visible light, is utilized as the ligand to coordinate with different types of metal ions, including Zn2+, Zr4+, and Ti4+, for construction of crystalline metal organic frameworks (MOFs). Impressively, when used as heterogeneous catalysts, all of the synthesized MOFs exhibit markedly enhanced activity. Furthermore, the asymmetric catalytic performance of these MOFs could be easily altered by selecting different metal ions, owing to the tunable electron transfer property between metal ions and chiral ligands. This work will provide a new approach for fabrication of heterogeneous catalysts and trigger more enthusiasm to conduct the asymmetric catalysis driven by visible light.

| S-EPMC5562422 | biostudies-other

Creating enzyme-mimicking nanopockets in metal-organic frameworks for catalysis.

Project description:Numerous efforts are being made toward constructing artificial nanopockets inside heterogeneous catalysts to implement challenging reactions that are difficult to occur on traditional heterogeneous catalysts. Here, the enzyme-mimetic nanopockets are fabricated inside the typical UiO-66 by coordinating zirconium nodes with terephthalate (BDC) ligands and monocarboxylate modulators including formic acid (FC), acetic acid (AC), or trifluoroacetic acid (TFA). When used in transfer hydrogenation of alkyl levulinates with isopropanol toward γ-valerolactone (GVL), these modulators endow zirconium sites with enhanced activity and selectivity and good stability. The catalytic activity of UiO-66FC is ~30 times that of UiO-66, also outperforming the state-of-the-art heterogeneous catalysts. Distinct from general consensus on electron-withdrawing or electron-donating effect on the altered activity of metal centers, this improvement mainly originates from the conformational change of modulators in the nanopocket to assist forming the rate-determining six-membered ring intermediate at zirconium sites, which are stabilized by van der Waals force interactions.

| S-EPMC9544332 | biostudies-literature

Electronic structure modulation of metal-organic frameworks for hybrid devices.

Project description:The study of metal-organic frameworks has largely been motivated by their structural and chemical diversity; however, these materials also possess rich physics, including optical, electronic, and magnetic activity. If these materials are to be employed in devices, it is necessary to develop an understanding of their solid-state behavior. We report an approach to calculate the effect of strain on the band structure of porous frameworks. The origin of the bidirectional absolute deformation potentials can be described from perturbations of the organic and inorganic building blocks. The unified approach allows us to propose several uses for hybrid materials, beyond their traditionally posited applications, including gas sensing, photoelectrochemistry, and as hybrid transistors.

| S-EPMC4284132 | biostudies-literature

Microfluidic Electrospray Niacin Metal-Organic Frameworks Encapsulated Microcapsules for Wound Healing.

Project description:Niacin metal-organic frameworks (MOFs) encapsulated microcapsules with alginate shells and copper-/zinc-niacin framework cores were in situ synthesized by using a microfluidic electrospray approach for wound healing. As the alginate shells were bacteria-responsively degradable, the niacin MOFs encapsulated microcapsules could intelligently, controllably, and programmably release calcium, copper, and zinc ions, depending on the degree of infections. The released ions could not only kill microbes by destroying their membrane and inducing the outflow of nutrient substance, but also activate copper/zinc superoxide dismutase (Cu/Zn-SOD) to eliminate oxygen free radicals and rescue the cells from oxidative stress injury. Furthermore, the simultaneously released niacin could promote hemangiectasis and absorption of functional metal ions. Thus, the niacin MOFs encapsulated microcapsules were imparted with outstanding antibacterial, antioxidant, and angiogenesis properties. Based on an in vivo study, we have also demonstrated that the chronic wound healing process of an infected full-thickness skin defect model could be significantly enhanced by using the niacin MOFs encapsulated microcapsules as therapeutic agent. Therefore, the microfluidic electrospray niacin MOFs encapsulated microcapsules are potential for clinical applications.

| S-EPMC6750103 | biostudies-literature

Metal-organic frameworks bonded with metal <i>N</i>-heterocyclic carbenes for efficient catalysis.

Project description:Metal N-heterocyclic carbenes (M-NHCs) on the pore walls of a porous metal-organic framework (MOF) can be used as active sites for efficient organic catalysis. Traditional approaches that need strong alkaline reagents or insoluble Ag2O are not, however, suitable for the incorporation of NHCs on the backbones of MOFs because such reagents could destroy their frameworks or result in low reactivity. Accordingly, development of facile strategies toward functional MOFs with covalently bound M-NHCs for catalysis is needed. Herein, we describe the development of a general and facile approach to preparing MOFs with covalently linked active M-NHC (M = Pd, Ir) single-site catalysts by using a soluble Ag salt AgOC(CF3)3 as the source and subsequent transmetalation. The well-defined M-NHC-MOF (M = Pd, Ir) catalysts obtained in this way have shown excellent catalytic activity and stability in Suzuki reactions and hydrogen transfer reactions. This provides a general and facile strategy for anchoring functional M-NHC single-site catalysts onto functionalized MOFs for different reactions.

| S-EPMC9270066 | biostudies-literature

Control of structural flexibility of layered-pillared metal-organic frameworks anchored at surfaces.

Project description:Flexible metal-organic frameworks (MOFs) are structurally flexible, porous, crystalline solids that show a structural transition in response to a stimulus. If MOF-based solid-state and microelectronic devices are to be capable of leveraging such structural flexibility, then the integration of MOF thin films into a device configuration is crucial. Here we report the targeted and precise anchoring of Cu-based alkylether-functionalised layered-pillared MOF crystallites onto substrates via stepwise liquid-phase epitaxy. The structural transformation during methanol sorption is monitored by in-situ grazing incidence X-ray diffraction. Interestingly, spatially-controlled anchoring of the flexible MOFs on the surface induces a distinct structural responsiveness which is different from the bulk powder and can be systematically controlled by varying the crystallite characteristics, for instance dimensions and orientation. This fundamental understanding of thin-film flexibility is of paramount importance for the rational design of MOF-based devices utilising the structural flexibility in specific applications such as selective sensors.

| S-EPMC6341086 | biostudies-literature

Transport Phenomena: Challenges and Opportunities for Molecular Catalysis in Metal-Organic Frameworks.

Project description:Metal-organic frameworks (MOFs) are appealing heterogeneous support matrices that can stabilize molecular catalysts for the electrochemical conversion of small molecules. However, moving from a homogeneous environment to a porous film necessitates the transport of both charge and substrate to the catalytic sites in an efficient manner. This presents a significant challenge in the application of such materials at scale, since these two transport phenomena (charge and mass transport) would need to operate faster than the intrinsic catalytic rate in order for the system to function efficiently. Thus, understanding the fundamental kinetics of MOF-based molecular catalysis of electrochemical reactions is of crucial importance. In this Perspective, we quantitatively dissect the interplay between the two transport phenomena and the catalytic reaction rate by applying models from closely related fields to MOF-based catalysis. The identification of the limiting process provides opportunities for optimization that are uniquely suited to MOFs due to their tunable molecular structure. This will help guide the rational design of efficient and high-performing catalytic MOF films with incorporated molecular catalyst for electrochemical energy conversion.

| S-EPMC7366383 | biostudies-literature

Retrofitting metal-organic frameworks.

Project description:The post-synthetic installation of linker molecules between open-metal sites (OMSs) and undercoordinated metal-nodes in a metal-organic framework (MOF) - retrofitting - has recently been discovered as a powerful tool to manipulate macroscopic properties such as the mechanical robustness and the thermal expansion behavior. So far, the choice of cross linkers (CLs) that are used in retrofitting experiments is based on qualitative considerations. Here, we present a low-cost computational framework that provides experimentalists with a tool for evaluating various CLs for retrofitting a given MOF system with OMSs. After applying our approach to the prototypical system CL@Cu3BTC2 (BTC = 1,3,5-benzentricarboxylate) the methodology was expanded to NOTT-100 and NOTT-101 MOFs, identifying several promising CLs for future CL@NOTT-100 and CL@NOTT-101 retrofitting experiments. The developed model is easily adaptable to other MOFs with OMSs and is set-up to be used by experimentalists, providing a guideline for the synthesis of new retrofitted MOFs with modified physicochemical properties.

| S-EPMC6820732 | 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