Amides Do Not Always Work: Observation of Guest Binding in an Amide-Functionalized Porous Metal-Organic Framework.
Ontology highlight
ABSTRACT:
SUBMITTER: Benson O
PROVIDER: S-EPMC5152937 | biostudies-literature |
REPOSITORIES: biostudies-literature
Similar Datasets
Project description:An azo-functionalized porous organic framework (denoted as JJU-1) was synthesized via FeCl3-promoted oxidative coupling polymerization. By virtue of a porous skeleton and a light/heat responsive azo functional group, this task-specific JJU-1 displays a reversible stimuli-responsive adsorption property triggered by UV irradiation and heat treatment. The initial Brunauer-Emmet-Teller (BET) surface area of this porous material is 467 m2 g-1. The CO2 sorption isotherms exhibit a slight decrease after UV irradiation because of the trans to cis conversion of the azo functional skeleton. It is worth mentioning that the responsive CO2 adsorption performance can be recycled for three cycles via alternating external stimuli, confirming the excellently reversible switchability of trans-to-cis isomerization and controllable CO2 adsorption.
| S-EPMC8398054 | biostudies-literature
Project description:Understanding the mechanism of gas-sorbent interactions is of fundamental importance for the design of improved gas storage materials. Here we report the binding domains of carbon dioxide and acetylene in a tetra-amide functionalized metal-organic framework, MFM-188, at crystallographic resolution. Although exhibiting moderate porosity, desolvated MFM-188a exhibits exceptionally high carbon dioxide and acetylene adsorption uptakes with the latter (232?cm3?g-1 at 295?K and 1?bar) being the highest value observed for porous solids under these conditions to the best of our knowledge. Neutron diffraction and inelastic neutron scattering studies enable the direct observation of the role of amide groups in substrate binding, representing an example of probing gas-amide binding interactions by such experiments. This study reveals that the combination of polyamide groups, open metal sites, appropriate pore geometry and cooperative binding between guest molecules is responsible for the high uptakes of acetylene and carbon dioxide in MFM-188a.
| S-EPMC5309720 | biostudies-literature
Project description:Designing porous materials which can selectively adsorb CO2 or CH4 is an important environmental and industrial goal which requires an understanding of the host-guest interactions involved at the atomic scale. Metal-organic polyhedra (MOPs) showing permanent porosity upon desolvation are rarely observed. We report a family of MOPs (Cu-1a, Cu-1b, Cu-2), which derive their permanent porosity from cavities between packed cages rather than from within the polyhedra. Thus, for Cu-1a, the void fraction outside the cages totals 56% with only 2% within. The relative stabilities of these MOP structures are rationalized by considering their weak nondirectional packing interactions using Hirshfeld surface analyses. The exceptional stability of Cu-1a enables a detailed structural investigation into the adsorption of CO2 and CH4 using in situ X-ray and neutron diffraction, coupled with DFT calculations. The primary binding sites for adsorbed CO2 and CH4 in Cu-1a are found to be the open metal sites and pockets defined by the faces of phenyl rings. More importantly, the structural analysis of a hydrated sample of Cu-1a reveals a strong hydrogen bond between the adsorbed CO2 molecule and the Cu(II)-bound water molecule, shedding light on previous empirical and theoretical observations that partial hydration of metal-organic framework (MOF) materials containing open metal sites increases their uptake of CO2. The results of the crystallographic study on MOP-gas binding have been rationalized using DFT calculations, yielding individual binding energies for the various pore environments of Cu-1a.
| S-EPMC7610226 | biostudies-literature
Project description:In order to develop new porous materials for applications in gas separations such as natural gas upgrading, landfill gas processing and acetylene purification it is vital to gain understanding of host-substrate interactions at a molecular level. Herein we report a series of six isoreticular metal-organic frameworks (MOFs) for selective gas adsorption. These materials do not incorporate open metal sites and thus provide an excellent platform to investigate the effect of the incorporation of ligand functionality via amide and alkyne groups on substrate binding. By reducing the length of the linker in our previously reported MFM-136, we report much improved CO2/CH4 (50?:?50) and CO2/N2 (15?:?85) selectivity values of 20.2 and 65.4, respectively (1 bar and 273 K), in the new amide-decorated MOF, MFM-126. The CO2 separation performance of MFM-126 has been confirmed by dynamic breakthrough experiments. In situ inelastic neutron scattering and synchrotron FT-IR microspectroscopy were employed to elucidate dynamic interactions of adsorbed CO2 molecules within MFM-126. Upon changing the functionality to an alkyne group in MFM-127, the CO2 uptake decreases but the C2H2 uptake increases by 68%, leading to excellent C2H2/CO2 and C2H2/CH4 selectivities of 3.7 and 21.2, respectively. Neutron powder diffraction enabled the direct observation of the preferred binding domains in MFM-126 and MFM-127, and, to the best of our knowledge, we report the first example of acetylene binding to an alkyne moiety in a porous material, with over 50% of the acetylene observed within MFM-127 displaying interactions (<4 Å) with the alkyne functionality of the framework.
| S-EPMC6346404 | biostudies-literature
Project description:Lithium tetrakis(4-boronatoaryl)borates were subjected to polycondensation reactions with selected polyhydroxyl monomers such as 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) and 2,3,6,7-tetrahydroxy-9,10-dimethylanthracene (THDMA). Obtained boronate-type ionic porous polymers TAB1-4 were characterized by PXRD, 6Li and 11B magic-angle spinning nuclear magnetic resonance (MAS NMR), FT-IR, SEM, and TGA. They exhibit relatively good sorption of H2 (up to 75 cm3/g STP), whereas N2 uptake at 77 K for lower pressure range is relatively poor (up to 50 cm3/g STP below P/P0 = 0.8). In addition, the effect of elongation of aryl arms in the tetraarylborate core on the materials' properties was studied. Thus, it was found that replacement of the 4-boronatophenyl with 4-boronatobiphenylyl group has a negative impact on the sorption characteristics.
| S-EPMC6630441 | biostudies-literature
Project description:It is of great significance to develop new materials for efficient capture cationic dyes methylene blue (MB) and malachite green (MG). In this work, a novel triptycene-based porous organic polymer with abundant thiol groups (TPP-SH) was prepared successfully by postmodification with a high surface area and robust triptycene-based porous organic polymer (TPP). The obtained TPP-SH exhibited a high surface area, good porosity, and good thermal stability. In addition, TPP-SH was highly effective at capturing MB and MG from aqueous solution because of the abundant thiols in its hierarchical structure. Under optimal adsorption conditions, the maximum adsorption capacities of MB and MG calculated by the Langmuir model at room temperature were 1146.3 and 689.6 mg g-1, respectively. These values are higher than those of many reported materials. The MB and MG adsorption rates were 0.0154 and 6.69 × 10-4 mg g-1 min-1, respectively. Furthermore, the polymer TPP-SH had a good recycling performance after adsorption-desorption at least five times. Therefore, the TPP-SH exhibited a high adsorption capacity, fast adsorption kinetics, and easy-recycling behavior, providing a new avenue for the preparation of green functionalized adsorbents with good performance for water decontamination.
| S-EPMC9161400 | biostudies-literature
Project description:Molecular-level interactions at organic-inorganic interfaces play crucial roles in many fields including catalysis, drug delivery, and geological mineral precipitation in the presence of organic matter. To seek insights into organic-inorganic interactions in porous framework materials, we investigated the phase evolution and energetics of confinement of a rigid organic guest, N,N,N-trimethyl-1-adamantammonium iodide (TMAAI), in inorganic porous silica frameworks (SSZ-24, MCM-41, and SBA-15) as a function of pore size (0.8 nm to 20.0 nm). We used hydrofluoric acid solution calorimetry to obtain the enthalpies of interaction between silica framework materials and TMAAI, and the values range from -56 to -177 kJ per mole of TMAAI. The phase evolution as a function of pore size was investigated by X-ray diffraction, IR, thermogravimetric differential scanning calorimetry, and solid-state NMR. The results suggest the existence of three types of inclusion depending on the pore size of the framework: single-molecule confinement in a small pore, multiple-molecule confinement/adsorption of an amorphous and possibly mobile assemblage of molecules near the pore walls, and nanocrystal confinement in the pore interior. These changes in structure probably represent equilibrium and minimize the free energy of the system for each pore size, as indicated by trends in the enthalpy of interaction and differential scanning calorimetry profiles, as well as the reversible changes in structure and mobility seen by variable temperature NMR.
| S-EPMC3918769 | biostudies-literature
Project description:Porous nanocrystals of metal-organic frameworks (MOFs) offer greater bioavailability, higher surface-to-volume ratios, superior control over MOF membrane fabrication, and enhanced guest-sorption kinetics compared to analogous bulk phases, but reliable synthesis of uniformly sized particles remains an outstanding challenge. Here, we identify the smallest and most probable sizes of known MOF nanocrystals and present an exhaustive comparative summary of nano- versus bulk-MOF syntheses. Based on critical analysis of reported size data and experimental conditions, an alternate to the LaMer model is proposed that describes nanocrystal formation as a kinetic competition between acid-base and metal-ligand reactivity. Particle growth terminates when ligands outcompete metal-ion diffusion, thereby arresting polymerization to produce kinetically trapped particle sizes. This model reconciles disparate trends in the literature and postulates that minimum particle sizes can be achieved by minimizing the relative ratios of metal-to-linker local concentrations. By identifying conditions that disfavor small nanocrystal sizes, this model also provides routes towards macroscopic MOF single crystals. A universal "seesaw" relationship between nanocrystal sizes and the concentrations of acidic surface-capping ligands provides a roadmap for achieving precise synthetic control. Best practices in synthesis, characterization, and data presentation are recommended for future investigations so that MOF nanocrystals may achieve their full potential as advanced nanomaterials.
| S-EPMC6979335 | biostudies-literature
Project description:Introducing porous material into optical cavities is a critical step toward the utilization of quantum-electrodynamical (QED) effects for advanced technologies, e.g. in the context of sensing. We demonstrate that crystalline, porous metal-organic frameworks (MOFs) are well suited for the fabrication of optical cavities. In going beyond functionalities offered by other materials, they allow for the reversible loading and release of guest species into and out of optical resonators. For an all-metal mirror-based Fabry-Perot cavity we yield strong coupling (∼21% Rabi splitting). This value is remarkably large, considering that the high porosity of the framework reduces the density of optically active moieties relative to the corresponding bulk structure by ∼60%. Such a strong response of a porous chromophoric scaffold could only be realized by employing silicon-phthalocyanine (SiPc) dyes designed to undergo strong J-aggregation when assembled into a MOF. Integration of the SiPc MOF as active component into the optical microcavity was realized by employing a layer-by-layer method. The new functionality opens up the possibility to reversibly and continuously tune QED devices and to use them as optical sensors.
| S-EPMC8163313 | biostudies-literature
Project description:A new Mg(ii) based photochromic porous metal-organic framework (MOF) has been synthesized bearing naphthalenediimide (NDI) chromophoric unit. This MOF (Mg-NDI) shows instant and reversible solvatochromic behavior in presence of solvents with different polarity. Mg-NDI also exhibits fast and reversible photochromism via radical formation. Due to the presence of electron deficient NDI moiety, this MOF exhibits selective organic amine (electron rich) sensing in solid state. The organic amine detection has been confirmed by photoluminescence quenching experiment and visual color change.
| S-EPMC5811159 | biostudies-literature