Evaporation-Induced Reticular Growth of UiO-66_NH in Chitosan Films: Adsorption of Iodine.

Metal-organic frameworks (MOFs) combined with polymers as hybrid materials offer numerous advantages such as enhanced performances through synergistic effects at their interface. The primary challenge in developing polymer/MOF hybrid matrix films is ensuring optimal dispersion and strong adhesion of crystalline MOFs to the polymer without aggregation, weak interaction, or phase separation. In this study, hierarchically porous UiO-66_NH/chitosan (ZrCSx-) films were designed by crystallizing UiO-66_NH within a chitosan (CS) skeleton.

Probing the water adsorption and stability under steam flow of Zr-based metal-organic frameworks using Zr solid-state NMR spectroscopy.

The stability of metal-organic frameworks (MOFs) in the presence of water is crucial for a wide range of applications, including the production of freshwater, desiccation, humidity control, heat pumps/chillers and capture and separation of gases. In particular, their stability under steam flow is essential since most industrial streams contain water vapor. Nevertheless, to the best of our knowledge, the stability under steam flow of Zr-based MOFs, which are among the most widely studied MOFs, has not been investigated so far.

Green synthesis of MOF-based textile composites for the degradation of a chemical warfare agent simulant.

A green synthesis of UiO-66-NH embedded in chitosan and deposited on textiles has been investigated for the degradation of chemical warfare agents. This method requires no heating or use of toxic solvents. The composite synthesized presents an interesting efficiency in detoxifying common simulants of chemical warfare agents, such as DMNP.

Probing oxygen exchange between UiO-66(Zr) MOF and water using O solid-state NMR.

The Zr-based Metal Organic Framework (MOF) UiO-66(Zr) is widely employed owing to its good thermal and chemical stabilities. Although the long-range structure of this MOF is preserved in the presence of water during several days, little is known about the formation of defects, which cannot be detected using diffraction techniques. We apply here O solid-state NMR spectroscopy at 18.

Identification of phosphorus sites in amorphous LiPON thin film by observing internuclear proximities.

Amorphous lithium phosphorus oxynitrides (LiPON), prepared by reactive magnetron sputtering, have become the electrolytes of choice for all-solid-state thin film microbatteries since its discovery in early 1990s. Nevertheless, there is still a lack of understanding of their atomic-level structure and its influence on ionic conductivity. Solid-state NMR spectroscopy represents a promising technique to determine the atomic-level structure of LiPON glasses but is challenging owing to its low sensitivity in the case of thin film materials.

Comparison of through-space homonuclear correlations between quadrupolar nuclei in solids.

Various two-dimensional (2D) homonuclear correlation experiments have been proposed to observe proximities between identical half-integer spin quadrupolar nuclei in solids. These experiments select either the single- or double-quantum coherences during the indirect evolution period, t. We compare here the efficiency and the robustness of the 2D double-quantum to single-quantum (DQ-SQ) and SQ-SQ homonuclear correlations for two half-integer spin quadrupolar isotopes subject to small chemical shift anisotropy (CSA): B with a nuclear spin I = 3/2 and Al with I = 5/2.

Capture and immobilization of gaseous ruthenium tetroxide RuO in the UiO-66-NH metal-organic framework.

Ru is a radioactive isotope usually generated by the nuclear industry within power plant reactors. During a nuclear accident, Ru reacts with oxygen, leading to the production of highly volatile ruthenium tetroxide RuO. The combination of volatility and radioactivity makes RuO, one of the most radiotoxic species and justifies the development of a specific setup for its capture and immobilization.

An unusual O/F distribution in the new pyrochlore oxyfluorides: NaBOF (B = Nb, Ta).

Two new oxyfluorides with a pyrochlore-type structure, NaNbOF and NaTaOF, have been obtained, for which the XRD crystallographic study coupled with F solid state NMR reveals an unusual O/F distribution. Both materials are n-type semiconductors exhibiting photoconductive properties.

Probing Si-O connectivities and proximities by solid-state NMR.

The measurement of dipolar and J- couplings between Si and O isotopes is challenging owing to (i) the low abundance of both isotopes and (ii) their close Larmor frequencies, which only differ by 19%. These issues are circumvented here by the use of isotopic enrichment and dedicated triple-resonance magic-angle spinning NMR probe. The surface of Si-enriched silica was labelled with O isotope and heated at 80 and 200 °C.

Characterization of Functional Groups in Estuarine Dissolved Organic Matter by DNP-enhanced N and C Solid-State NMR.

Estuaries are key ecosystems with unique biodiversity and are of high economic importance. Along the estuaries, variations in environmental parameters, such as salinity and light penetration, can modify the characteristics of dissolved organic matter (DOM). Nevertheless, there is still limited information about the atomic-level transformations of DOM in this ecosystem.

Improved NMR transfer of magnetization from protons to half-integer spin quadrupolar nuclei at moderate and high magic-angle spinning frequencies.

Half-integer spin quadrupolar nuclei are the only magnetic isotopes for the majority of the chemical elements. Therefore, the transfer of polarization from protons to these isotopes under magic-angle spinning (MAS) can provide precious insights into the interatomic proximities in hydrogen-containing solids, including organic, hybrid, nanostructured and biological solids. This transfer has recently been combined with dynamic nuclear polarization (DNP) in order to enhance the NMR signal of half-integer quadrupolar isotopes.

Recent developments in MAS DNP-NMR of materials.

Solid-state NMR spectroscopy is a powerful technique for the characterization of the atomic-level structure and dynamics of materials. Nevertheless, the use of this technique is often limited by its lack of sensitivity, which can prevent the observation of surfaces, defects or insensitive isotopes. Dynamic Nuclear Polarization (DNP) has been shown to improve by one to three orders of magnitude the sensitivity of NMR experiments on materials under Magic-Angle Spinning (MAS), at static magnetic field B ≥ 5 T, conditions allowing for the acquisition of high-resolution spectra.

Grafting of a new bis-silylamido aluminum species on silica: insight from solid-state NMR into interactions with the surface.

The new bisamido aluminum species [AlCl{N(SiMe3)2}2(THF)] (1) was prepared and fully characterized by 27Al and 35Cl solid-state NMR, along with X-ray diffraction studies. 1 was grafted on silica partially dehydroxylated at 700 °C, affording silica-supported Al species. The resulting material (2) was characterized by IR, elemental analysis and 1H, 13C and 27Al solid-state MAS NMR.

Magnetization transfer from protons to quadrupolar nuclei in solid-state NMR using PRESTO or dipolar-mediated refocused INEPT methods.

In solid-state NMR spectroscopy, the through-space transfer of magnetization from protons to quadrupolar nuclei is employed to probe proximities between those isotopes. Furthermore, such transfer, in conjunction with Dynamic Nuclear Polarization (DNP), can enhance the NMR sensitivity of quadrupolar nuclei, as it allows the transfer of DNP-enhanced H polarization to surrounding nuclei. We compare here the performances of two approaches to achieve such transfer: PRESTO (Phase-shifted Recoupling Effects a Smooth Transfer of Order), which is currently the method of choice to achieve the magnetization transfer from protons to quadrupolar nuclei and which has been shown to supersede Cross-Polarization under Magic-Angle Spinning (MAS) for quadrupolar nuclei and D-RINEPT (Dipolar-mediated Refocused Insensitive Nuclei Enhanced by Polarization Transfer) using symmetry-based SR4 recoupling, which has already been employed to transfer the magnetization in the reverse way from half-integer quadrupolar spin to protons.

Imaging the spatial distribution of radiofrequency field, sample and temperature in MAS NMR rotor.

We investigate using nutation experiments the spatial distribution of radiofrequency (rf) field, sample, temperature and cross-polarization transfer efficiency in 1.3 mm rotor. First, two-dimensional (2D) H nutation experiments on silicone thin cylinders in the presence of B field gradient generated by shim coils are used to image the spatial distribution of rf field inside the rotor.

On the use of solid-state Sc NMR for structural investigations of molecular and silica-supported scandium amide catalysts.

Tris- and tetra-coordinated scandium amides were grafted onto silica and probed as catalysts for alkyne dimerization. Sc NMR was carried out, providing information about the metal coordination sphere. The increasing number of coordinated ligands was correlated with decreased catalytic activity.

Ga-Se connectivities and proximities in gallium selenide crystal and glass probed by solid-state NMR.

We introduce two-dimensional (2D) Ga-Se through-bond and through-space correlation experiments. Such correlations are achieved using (i) the J-mediated Refocused Insensitive Nuclei Enhanced by Polarization Transfer (J-RINEPT) method with Ga excitation and Se Carr-Purcell-Meiboon-Gill (CPMG) detection, as well as (ii) the J- or dipolar-mediated Hetero-nuclear Multiple-Quantum Correlation (J- or D-HMQC) schemes with Ga excitation and quadrupolar CPMG (QCPMG) detection. These methods are applied to the crystalline β-GaSe and the 0.

γ-Independent through-space hetero-nuclear correlation between spin-1/2 and quadrupolar nuclei in solids.

We introduce novel sequences using indirect detection to correlate quadrupolar nuclei and spin-1/2 isotopes, other than H and F. These sequences use γ-encoded symmetry-based RN schemes that reintroduce the space component |m| = 1 of the heteronuclear dipolar coupling. These schemes can be applied to the indirectly detected spin in Dipolar-mediated Heteronuclear Multiple-Quantum Correlation (D-HMQC) sequence or to the detected isotope in a novel sequence, named Dipolar-mediated Heteronuclear Universal-Quantum Correlation (D-HUQC).

Solid-State NMR Spectroscopy Proves the Presence of Penta-coordinated Sc Sites in MIL-100(Sc).

Advanced solid-state NMR methods and first-principles calculations demonstrate for the first time the formation of penta-coordinated scandium sites. These coordinatively unsaturated sites were shown during the thermal activation of scandium-based metal-organic frameworks (MOFs). A Sc NMR experiment allows their specific observation in activated Sc BTB (H BTB=1,3,5-tris(4-carboxyphenyl)benzene) and MIL-100(Sc) MOFs.

3D correlation NMR spectrum between three distinct heteronuclei for the characterization of inorganic samples: Application on sodium alumino-phosphate materials.

We report here an original NMR sequence allowing the acquisition of 3D correlation NMR spectra between three distinct heteronuclei, among which two are half-integer spin quadrupolar nuclei. Furthermore, as two of them exhibit close Larmor frequency, this experiment was acquired using a standard triple-resonance probe equipped with a commercial frequency splitter. This NMR technique was tested and applied to sodium alumino-phosphate compounds with P as the spin-1/2 nucleus and Na and Al as the close Larmor frequencies isotopes.

Local measure of the electromagnetic field in magnetic resonance coils: How do simulations help to disentangle the contributions of the electric and magnetic fields?

The development of probes for Nuclear Magnetic Resonance (NMR) spectroscopy of metabolites, biomolecules or materials requires the accurate determination of the radio-frequency (RF) magnetic field strength, B, at the position of the sample since this RF-field strength is related to the signal sensitivity and the excitation bandwidth. The Ball Shift (BS) technique is a commonly employed test bench method to measure the B value. Nevertheless, the influence of the RF electric field, E, on BS is often overlooked.

Stability of metal-organic frameworks under gamma irradiation.

We report the study of the resistance of archetypal MOFs (MILs, HKUST-1, UiO-66, and ZIF-8) under gamma irradiation. The different porous solids were irradiated with doses up to 1.75 MGy.

Solid-state NMR indirect detection of nuclei experiencing large anisotropic interactions using spinning sideband-selective pulses.

Under Magic-Angle Spinning (MAS), a long radio-frequency (rf) pulse applied on resonance achieves the selective excitation of the center-band of a wide NMR spectrum. We show herein that these rf pulses can be applied on the indirect channel of Hetero-nuclear Multiple-Quantum Correlation (HMQC) sequences, which facilitate the indirect detection via spin-1/2 isotopes of nuclei exhibiting wide spectra. Numerical simulations show that this indirect excitation method is applicable to spin-1/2 nuclei experiencing a large chemical shift anisotropy, as well as to spin-1 isotopes subject to a large quadrupole interaction, such as (14)N.