RESUMEN
Introduction of a dielectric material in a nuclear magnetic resonance (NMR) probe head modifies the frequency response of the probe circuit, a phenomenon revealed by detuning of the probe. For NMR spectroscopy, this detuning is corrected for by tuning and matching the probe head prior to the NMR measurement. The magnitude of the probe detuning, "the dielectric shift", provides direct access to the dielectric properties of the sample, enabling NMR spectrometers to simultaneously perform both dielectric and NMR spectroscopy. By measuring sample dielectric permittivity as a function of frequency, dielectric permittivity spectroscopy can be performed using the new methodology. As a proof of concept, this was evaluated on methanol, ethanol, 1-propanol, 1-pentanol, and 1-octanol using a commercial cross-polarization magic angle spinning (CPMAS) NMR probe head. The results accurately match the literature data collected by standard dielectric spectroscopy techniques. Subsequently, the method was also applied to investigate the solvent-surface interactions of water confined in the micropores of an MFI-type, hydrophilic zeolite with a Si/Al ratio of 11.5. In the micropores, water adsorbs to BroÌ·nsted acid sites and defect sites, resulting in a drastically decreased dielectric permittivity of the nanoconfined water. Theoretical background for the new methodology is provided using an effective electric circuit model of a CPMAS probe head with a solenoid coil, describing the detuning resulting from the insertion of dielectric samples in the probe head.
RESUMEN
The photoluminescence properties (PL) of Eu3+ hosted in the hydroxide layers of layered double hydroxides (LDHs) enables calibrationless quantification of anions in the interlayers. The concept is demonstrated during the nitrate-to-carbonate ion exchange in Zn2+/Al3+/Eu3+ LDHs and can be implemented as a remote optical sensor to detect intrusion of anions such as Cl- or CO32-.
RESUMEN
Upon liquid phase adsorption of C1-C5 primary alcohols on high silica MFI zeolites (Si/Al = 11.5-140), the concentration of adsorbed molecules largely exceeds the concentration of traditional adsorption sites: Brønsted acid and defect sites. Combining quantitative in situ1H MAS NMR, qualitative multinuclear NMR and IR spectroscopy, hydrogen bonding of the alcohol function to oxygen atoms of the zeolite siloxane bridges (Si-O-Si) was shown to drive the additional adsorption. This mechanism co-exists with chemi- and physi-sorption on Brønsted acid and defect sites and does not exclude cooperative effects from dispersive interactions.
RESUMEN
Synthesis of layered materials exhibiting hierarchical porosity remains challenging, but nevertheless worthwhile because it turns such solids into functional materials with high specific surface area. Using a soft-templating strategy in combination with the incorporation of 8-fold coordinated Eu3+, self-assembly of self-supported layered double hydroxide (LDH) nanotubes has been achieved. Heteromorphic equimolar substitution of Al3+ by Eu3+ in Zn2+/Al3+ LDH solids intercalated with 1,3,5-benzenetricarboxylate anions (BTC) assists precipitation of the double hydroxide layers onto the convex surface of Pluronic® P-123 worm-like micelles, yielding multilayer cylinders of BTC-intercalated LDHs. Removal of the micellar template is easily achieved by liquid extraction with methanol, yielding a network of interconnected, well-defined, self-supported, multi-walled, hollow cylindrical nanotubes. Removal of Eu3+ from the synthesis disables formation of the nanotubular morphology, but still yields LDHs containing a network of embedded mesopores, resulting in a specific surface area that is 5-fold higher as compared to standard LDHs.
RESUMEN
Herein, we report a class of novel lanthanide-doped self-supported layered double hydroxide (LDH) nanotubes featuring a combination of micro- and mesoporosity. The synthesis of the nanotubes has been achieved by a soft-templating strategy. Incorporation of La3+, Pr3+, Nd3+, Sm3+, Eu3+, Gd3+ or Tb3+ in the LDHs assisted the self-assembly of the double hydroxide layers onto the surface of Pluronic P-123 worm-like micelles, enabling the formation of the nanotubes. Removal of the micellar template provides accessibility to the mesopores, yielding a network of hollow cylindrical nanotubes with internal diameter of about 10 nm. An antenna molecule (benzene-1,3,5-tricarboxylate, BTC) is hosted in their 1-nanometre-wide micropores. Upon UV excitation, the nanotubes emit light in a set of wavelengths ranging from the ultraviolet to the infrared.
RESUMEN
Luminescent layered double hydroxides (LDH) intercalated by isophthalate (ISO) and nitrilotriacetate (NTA) have been synthesized and characterized by powder X-ray diffraction (PXRD), extended X-ray absorption fine structure (EXAFS), elemental analysis (ICP-OES and CHN), and photoluminescence spectroscopy. While PXRD shows the successful formation of ZnAlEu LDHs, EXAFS reveals that the Eu activators are hosted in the hydroxide layers with an eightfold, oxygen-rich coordination, distinct from the sixfold coordination expected for the octahedral sites of metal cations in LDHs. This kind of coordination should locally distort the brucite-like layers. Additionally, the intercalation of ISO and NTA in the LDHs is shown to change the coordination environment around Eu compared to nitrate-intercalated ZnAlEu LDHs, which suggests that these anions directly interact with the Eu centers and/or strongly affect their coordination geometry. Finally, from the photoluminescence results, analyzed based on the Judd-Ofelt theory, it is determined that Eu is most likely in an environment with no inversion symmetry.
RESUMEN
Self-supported oligo-layered ZnAlEu LDH nanotubes (∅ 20 nm) self-assemble upon controlled hydrolysis of the metal ions (Zn2+, Al3+, Eu3+) in the presence of 1,3,5-benzenetricarboxylate anions and non-ionic worm-like micelles. Their high surface area and easily accessible cylindrical mesopores (175 m2 g-1; 0.75 cm3 g-1) facilitate interaction with 5 nm CdTe quantum dots, enhancing the overall luminescence behavior.
