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 17 O solid-state NMR spectroscopy at 18.8â T to investigate the reactivity of UiO-66, through the exchange of oxygen atoms between the different sites of the MOF and water. For that purpose, we have selectively enriched in 17 O isotope the carboxylate groups of UiO-66(Zr) by using it with 17 O-labeled terephthalic acid prepared using mechanochemistry. In the presence of water at 50 °C and a following dehydration at 150 °C, we observe an overall exchange of O atoms between COO- and µ3 -O2- sites. Furthermore, we demonstrate that the three distinct oxygen sites, µ3 -OH, µ3 -O2- and COO- , of UiO-66(Zr) MOF can be enriched in 17 O isotope by post-synthetic hydrothermal treatment in the presence of 17 O-enriched water. These results demonstrate the lability of Zr-O bonds and the reactivity of UiO-66(Zr) with water.
A simple and versatile preparation of Zn(II)-poly(carboxylates) reticulated binders by the addition of Zn(II) precursors (ZnSO4, ZnO, or Zn(NO3)2) into a preoptimized poly(carboxylic acids) binder solution is proposed. These binders lead systematically to a significantly improved electrochemical performance when used for the formulation of silicon-based negative electrodes. The formation of carboxylate-Zn(II) coordination bonds formation is investigated by rheology and FTIR and NMR spectroscopies. Mechanical characterizations reveal that the coordinated binder offers a better electrode coating cohesion and adhesion to the current collector, as well as higher hardness and elastic modulus, which are even preserved in the presence of a carbonate solvent (i.e., in battery operation conditions). Ultimately, as shown from operando dilatometry experiments, the electrode expansion during lithiation is reduced, mitigating electrode mechanical failure. Such coordinatively reticulated electrodes outperform their uncoordinated counterparts with an improved capacity retention of over 30% after 60 cycles.
We present a new operando approach for following reactions taking place in mechanochemistry, relying on the analysis of the evolution of the sound during milling. We show that differences in sound can be directly correlated to (physico)chemical changes in the reactor, making this technique highly attractive and complementary to others for monitoring mechanochemical reactions. Most notably, it can provide unique information on the actual movements of the beads within the milling jars, which opens new avenues for helping rationalize mechanochemical processes.
Oxygen-17 and deuterium are two quadrupolar nuclei that are of interest for studying the structure and dynamics of materials by solid-state nuclear magnetic resonance (NMR). Here, 17 O and 2 H NMR analyses of crystalline ibuprofen and terephthalic acid are reported. First, improved 17 O-labelling protocols of these molecules are described using mechanochemistry. Then, dynamics occurring around the carboxylic groups of ibuprofen are studied considering variable temperature 17 O and 2 H NMR data, as well as computational modelling (including molecular dynamics simulations). More specifically, motions related to the concerted double proton jump and the 180° flip of the H-bonded (-COOH)2 unit in the crystal structure were looked into, and it was found that the merging of the C=O and C-OH 17 O resonances at high temperatures cannot be explained by the sole presence of one of these motions. Lastly, preliminary experiments were performed with a 2 H-17 O diplexer connected to the probe. Such configurations can allow, among others, 2 H and 17 O NMR spectra to be recorded at different temperatures without needing to tune or to change probe configurations. Overall, this work offers a few leads which could be of use in future studies of other materials using 17 O and 2 H NMR.
Fatty acids are ubiquitous in biological systems and widely used in materials science, including for the formulation of drugs and the surface-functionalization of nanoparticles. However, important questions regarding the structure and reactivity of these molecules are still to be elucidated, including their mode of binding to certain metal cations or materials surfaces. In this context, we have developed novel, efficient, user-friendly, and cost-effective synthetic protocols based on ball-milling, for the 17O and 18O isotopic labeling of two key fatty acids which are widely used in (nano)materials science, namely stearic and oleic acid. Labeled molecules were analyzed by 1H and 13C solution NMR, IR spectroscopy, and mass spectrometry (ESI-TOF and LC-MS), as well as 17O solid state NMR (for the 17O labeled species). In both cases, the labeling procedures were scaled-up to produce up to gram quantities of 17O- or 18O-enriched molecules in just half-a-day, with very good synthetic yields (all ≥84%) and enrichment levels (up to an average of 46% per carboxylic oxygen). The 17O-labeled oleic acid was then used for the synthesis of a metal soap (Zn-oleate) and the surface-functionalization of ZnO nanoparticles (NPs), which were characterized for the first time by high-resolution 17O NMR (at 14.1 and 35.2 T). This allowed very detailed insight into (i) the coordination mode of the oleate ligand in Zn-oleate to be achieved (including information on Zn···O distances) and (ii) the mode of attachment of oleic-acid at the surface of ZnO (including novel information on its photoreactivity upon UV-irradiation). Overall, this work demonstrates the high interest of these fatty acid-enrichment protocols for understanding the structure and reactivity of a variety of functional (nano)materials systems using high resolution analyses like 17O NMR.
Nanostructures/chemistry , Oleic Acid/chemistry , Oxygen Isotopes/chemistry , Stearic Acids/chemistry , Isotope Labeling , Magnetic Resonance Spectroscopy
