Browse
Submit Data
Databases
API
Help

Dataset Information

31 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Metal-Organic Frameworks as Versatile Heterogeneous Solid Catalysts for Henry Reactions.

ABSTRACT: Metal-organic frameworks (MOFs) have become one of the versatile solid materials used for a wide range of applications, such as gas storage, gas separation, proton conductivity, sensors and catalysis. Among these fields, one of the more well-studied areas is the use of MOFs as heterogeneous catalysts for a broad range of organic reactions. In the present review, the employment of MOFs as solid catalysts for the Henry reaction is discussed, and the available literature data from the last decade are grouped. The review is organized with a brief introduction of the importance of Henry reactions and structural properties of MOFs that are suitable for catalysis. The second part of the review discusses the use of MOFs as solid catalysts for the Henry reaction involving metal nodes as active sites, while the third section provides data utilizing basic sites (primary amine, secondary amine, amides and urea-donating sites). While commenting on the catalytic results in these two sections, the advantage of MOFs over other solid catalysts is compared in terms of activity by providing turnover number (TON) values and the structural stability of MOFs during the course of the reaction. The final section provides our views on further directions in this field.

SUBMITTER: Cirujano FG

PROVIDER: S-EPMC7962073 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Porphyrin-Based Metal-Organic Frameworks as Heterogeneous Catalysts in Oxidation Reactions.

Project description:Porphyrin-based Metal-Organic Frameworks (Por-MOFs) constitute a special branch of the wide MOF family that has proven its own value and high potential in different applications. In this mini-review the application of these materials as catalysts in oxidation reactions is highlighted.

| S-EPMC6273352 | biostudies-literature

Heterogeneous Nickel Catalysts Derived from 2D Metal-Organic Frameworks for Regulating the Selectivity of Furfural Hydrogenation.

Project description:Hydrolysis of the biomass platform compound furfural can produce a bulk of fine chemicals because of its multiple functional groups. Developing an efficient catalytic system to regulate the process toward some desirable products has always been a hot research area. Herein, the novel Ni-based catalysts (Ni-MFC-X, X = 300, 400...800) synthesized by pyrolysis of the 2D Ni-based metal-organic framework (MOF) in the temperature range 300-800 °C show good performance for selective hydrogenation of furfural (FUR). Interestingly, the calcination temperature of the MOF precursor plays an important role in hydrogenation of furfural with controllable selectivity toward furfuryl alcohol (FOL) and tetrahydro FOL (THFOL). Ni-MFC-500 affords us 92.5% conversion of furfural and 59.5% selectivity of FOL. Ni-MFC-700 can promote hydrogenation of furfural with 91.8% conversion and 51.0% selectivity of THFOL. Furthermore, the stability of as-obtained Ni-MFC-500 and Ni-MFC-700 was also very impressive in this reaction system.

| S-EPMC6933581 | biostudies-literature

Triphenylphosphine-Based Covalent Organic Frameworks and Heterogeneous Rh-P-COFs Catalysts.

Project description:The synthesis of phosphine-based functional covalent organic frameworks (COFs) has attracted great attention recently. Herein, we present two examples of triphenylphosphine-based COFs (termed P-COFs) with well-defined crystalline structures, high specific surface areas, and good thermal stability. Furthermore, rhodium catalysts with these P-COFs as support material show high turnover frequency for the hydroformylation of olefins, as well as excellent recycling performance. This work not only extends the phosphine-based COF family, but also demonstrates their application in immobilizing homogeneous metal-based (e.g., Rh-phosphine) catalysts for application in heterogeneous catalysis.

| S-EPMC7540510 | biostudies-literature

Postsynthetic modification: a versatile approach toward multifunctional metal-organic frameworks.

Project description:An isoreticular metal-organic framework (IRMOF-3) containing 2-amino-1,4-benzenedicarboxylic acid (NH(2)-BDC) as a building block is shown to undergo chemical modification with a diverse series of anhydrides and isocyanates. The modification of IRMOF-3 by these reagents has been evidenced by using a variety of methods, including NMR and electrospray ionization mass spectrometry, and the structural integrity of the modified MOFs has been confirmed by thermogravimetric analysis, powder X-ray diffraction, and gas sorption analysis. The results show that a variety of functional groups can be introduced onto the MOF including amines, carboxylic acids, and chiral groups. Furthermore, it is shown that tert-butyl-based asymmetric anhydrides can be used to selectively deliver chemical payloads to the IRMOF. Finally, the results demonstrate that at least four different chemical modifications can be performed on IRMOF-3 and that the reaction conditions can be modulated to control the relative abundance of each group. The findings presented here demonstrate several important features of postsynthetic modification on IRMOF-3, including (1) facile introduction of a wide range of functional groups using simple reagents (e.g., anhydrides and isocyanates), (2) the introduction of multiple (as many as four different) substituents into the MOF lattice, and (3) control over reaction conditions to preserve the crystallinity and microporosity of the resultant MOFs. The findings clearly illustrate that postsynthetic modification represents a powerful means to access new MOF compounds with unprecedented chemical complexity, which may serve as the basis of multifunctional materials.

| S-EPMC2924877 | biostudies-literature

Metal-Organic Frameworks as Formose Reaction Catalysts with Enhanced Selectivity.

Project description:The formose reaction is an autocatalytic series of aldol condensations that allows one to obtain monosaccharides from formaldehyde. The formose reaction suffers from a lack of selectivity, which hinders practical applications at the industrial level. Over the years, many attempts have been made to overcome this selectivity issue, with modest results. Heterogeneous porous catalysts with acid-base properties, such as Metal-Organic Frameworks (MOFs), can offer advantages compared to homogeneous strong bases (e.g., calcium hydroxide) for increasing the selectivity of this important reaction. For the very first time, four different Zeolite Imidazolate Frameworks are presented in this work as catalysts for the formose reaction in liquid phase, and their catalytic performances were compared with those of the typical homogeneous catalyst (i.e., calcium hydroxide). The heterogeneous nature of the catalysis, the possible contribution of leached metal or linkers to the solution, and the stability of the materials were investigated. The porous structure of these solids and their mild basicity make them suitable for obtaining enhanced selectivity at 30% formaldehyde conversion. Most of the MOFs tested showed low structural stability under reaction conditions, thereby indicating the need to search for new MOF families with higher robustness. However, this important result opens the path for future research on porous heterogeneous basic catalysts for the formose reaction.

| S-EPMC10458508 | biostudies-literature

Versatile, high quality and scalable continuous flow production of metal-organic frameworks.

Project description:Further deployment of Metal-Organic Frameworks in applied settings requires their ready preparation at scale. Expansion of typical batch processes can lead to unsuccessful or low quality synthesis for some systems. Here we report how continuous flow chemistry can be adapted as a versatile route to a range of MOFs, by emulating conditions of lab-scale batch synthesis. This delivers ready synthesis of three different MOFs, with surface areas that closely match theoretical maxima, with production rates of 60?g/h at extremely high space-time yields.

| S-EPMC4069692 | biostudies-literature

Transition Metal Oxodiperoxo Complex Modified Metal-Organic Frameworks as Catalysts for the Selective Oxidation of Cyclohexane.

Project description:In this work, a series of modified metal-organic frameworks (MOFs) have been prepared by pre- and post-treatment with transition metal oxodiperoxo complexes (MoO(O2)2, WO(O2)2, and KVO(O2)2). The obtained materials are characterized by XRD, FTIR, SEM, TEM, inductively coupled plasma atomic emission spectrometry (ICP-AES), and X-ray photoelectron spectroscopy (XPS), as well as by N2 adsorption/desorption measurement. The characterization results show that transition metal oxodiperoxo complexes are uniformly incorporated into the MOF materials without changing the basic structures. The performance of cyclohexane oxidation on metal oxodiperoxo complex modified MOFs are evaluated. UiO-67-KVO(O2)2 shows the best performance for cyclohexane oxidation, with 78% selectivity to KA oil (KA oil refers to a cyclohexanol and cyclohexanone mixture) at 9.4% conversion. The KA selectivity is found to depend on reaction time, while hot-filtration experiments indicates that the catalytic process is heterogeneous with no leaching of metal species.

| S-EPMC7078608 | biostudies-literature

Gas reactions under intrapore condensation regime within tailored metal-organic framework catalysts.

Project description:Production of 1-butene, a major monomer in polymer industry, is dominated by homogeneous protocols via ethylene dimerization. Homogeneous catalysts can achieve high selectivity but require large amounts of activators and solvents, and exhibit poor recyclability; in turn, heterogeneous systems are robust but lack selectivity. Here we show how the precise engineering of metal-organic frameworks (MOFs) holds promise for a sustainable process. The key to the (Ru)HKUST-1 MOF activity is the intrapore reactant condensation that enhances ethylene dimerization with high selectivity (> 99% 1-butene) and high stability (> 120 h) in the absence of activators and solvents. According to spectroscopy, kinetics, and modeling, the engineering of defective nodes via controlled thermal approaches rules the activity, while intrapore ethylene condensation accounts for selectivity and stability. The combination of well-defined actives sites with the concentration effect arising from condensation regimes paves the way toward the development of robust MOF catalysts for diverse gas-phase reactions.

| S-EPMC6502813 | biostudies-literature

Sulfate Radical-Based Degradation of Organic Pollutants: A Review on Application of Metal-Organic Frameworks as Catalysts.

Project description:The degradation of organic pollutants present in domestic and industrial effluents is a matter of concern because of their high persistence and ecotoxicity. Recently, advanced oxidation processes (AOPs) are being emphasized for organic pollutant removal from effluents, as they have shown higher degradation efficiencies when compared to conventional activated sludge processes. Sulfate radical-based methods are some of the AOPs, mainly carried out using persulfate (PS) and peroxymonosulfate (PMS), which have gained attention due to the ease of sulfate radical generation and the effective degradation of organic molecules. PMS is gaining more popularity because of its high reactivity and ability to generate excess sulfate radicals. PMS has been the major focus; therefore, its mechanism has been explained, and limitations have been elaborated. The involvement of metal-organic frameworks for PMS/PS activation applied to organic pollutant removal and recent advances in the application of biochar and hydrogel-assisted metal-organic frameworks have been discussed.

| S-EPMC10536895 | biostudies-literature

Hierarchically encapsulating enzymes with multi-shelled metal-organic frameworks for tandem biocatalytic reactions.

Project description:Biocatalytic transformations in living organisms, such as multi-enzyme catalytic cascades, proceed in different cellular membrane-compartmentalized organelles with high efficiency. Nevertheless, it remains challenging to mimicking biocatalytic cascade processes in natural systems. Herein, we demonstrate that multi-shelled metal-organic frameworks (MOFs) can be used as a hierarchical scaffold to spatially organize enzymes on nanoscale to enhance cascade catalytic efficiency. Encapsulating multi-enzymes with multi-shelled MOFs by epitaxial shell-by-shell overgrowth leads to 5.8~13.5-fold enhancements in catalytic efficiencies compared with free enzymes in solution. Importantly, multi-shelled MOFs can act as a multi-spatial-compartmental nanoreactor that allows physically compartmentalize multiple enzymes in a single MOF nanoparticle for operating incompatible tandem biocatalytic reaction in one pot. Additionally, we use nanoscale Fourier transform infrared (nano-FTIR) spectroscopy to resolve nanoscale heterogeneity of vibrational activity associated to enzymes encapsulated in multi-shelled MOFs. Furthermore, multi-shelled MOFs enable facile control of multi-enzyme positions according to specific tandem reaction routes, in which close positioning of enzyme-1-loaded and enzyme-2-loaded shells along the inner-to-outer shells could effectively facilitate mass transportation to promote efficient tandem biocatalytic reaction. This work is anticipated to shed new light on designing efficient multi-enzyme catalytic cascades to encourage applications in many chemical and pharmaceutical industrial processes.

| S-EPMC8758787 | 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