The influence of additives on the reaction kinetics and for microstructure refinement in LiBH 4-MgH 2 composites is investigated in detail. Indications on the rate limiting processes during the reactions are obtained by comparison of the measured reaction kinetics to simulations with one specific rate limiting process. The kinetics of the sorption reactions are derived from volumetric measurements as well as from in-situ Xray diffraction (XRD) measurements. During desorption, the hydrogen is released at a constant rate, which possibly is correlated to the one-dimensional growth of MgB 2 platelets. In contrast, the kinetic curves of the absorption reactions exhibit the typical shape of contracting-volume controlled kinetics. The microscopical interpretation of kinetic measurements are supported by transmission electron microscopy (TEM) images confirming the formation of additive-nanostructures in the grain boundaries upon cycling. The present investigations underline the importance of the additives as nucleation substrates and the influence of the microstructure on the reaction kinetics.
Chiral lanthanide cages with circularly polarized luminescence (CPL) properties have found potential application in enantioselective guest recognition and sensing. However, it still remains a big challenge to develop a simple and robust method for the diastereoselective assembly of homochiral lanthanide cages in view of the large lability of the Ln(III) ions. Herein, we report the first example of the formation of a enantiopure lanthanide tetrahedral cage via a chiral ancillary ligand induction strategy. One such cage, (Eu 4 L 4 )(R/S-BINAPO) 4 , is assembled by four achiral C 3 -symmeric tris(βdiketones) (4,4′,4″-tris(4,4,4-trifluoro-1,3-dioxobutyl)triphenylamine, L) as faces, four Eu(III) ions as vertices and four chiral R-/S-bis(diphenylphosphoryl)-1,1′-binaphthyl (R/S-BINAPO) as ancillary ligands. X-ray crystallography and NMR and CD spectra confirm the formation of a pair of enantiopure chiral topological tetrahedral cages, (Eu 4 L 4 )(R-BINAPO) 4 and (Eu 4 L 4 )(S-BINAPO) 4 (ΔΔΔΔ-1 and ΛΛΛΛ-1). As expected, the tetrahedral cages present strong CPL with |g lum | values up to 0.20, while they unexpectedly give ultrahigh luminescent quantum yields (QYs) of up to 81%, the highest value reported in chiral Ln(III) complexes. More impressively, the chiral memory effect for a lanthanide-based assembly is observed for the first time. The chirality of the original cage 1 framework is retained after R/S-BINAPO is replaced by the achiral bis[2-(diphenylphosphino)phenyl] ether oxide (DPEPO), and thus another pair of enantiopure Eu(III) tetrahedral cages, ΔΔΔΔand ΛΛΛΛ-[(Eu 4 L 4 )(DPEPO) 4 ] (ΔΔΔΔ-2 and ΛΛΛΛ-2), have been isolated. Encouragingly, cage 2 also presents an impressive luminescence quantum yield (QY = 68%) and intense CPL (|g lum | = 0.11). This study offers a simple and low-cost synthesis strategy for the preparation of lanthanide cages with CPL properties.
Because of the involvement
of the gas–solid diffusion, device
fabrication, and the relatively complex photophysical process, the
lanthanide complexes are rarely exploited as fluorescence sensors
for volatile compound (VC) detection. Herein, we report the first
example of a discrete 3D Ln-based architecture as a sensor for VCs.
The designed Eu4L4 tetrahedral cage shows highly
selective, rapidly reversible, and turn-on emissive responses toward
volatile amines/NH3 in a spin-coated film. Through the
comprehensive spectral characteristic and density functional theory
calculation, an intermolecular weak nucleophilic interaction is proposed
for this response mechanism. Combining this weak interactions with
the permeability of the cage, the film presents subsecond to second
timescales rapid response; combining the fitting electrophilic capability
of the β-diketonate units to amine nitrogen with the tunable
intramolecular charge-transfer feature, the cage shows excellent selectivity
and turn-on emissive response. This work provides a new clue to develop
the lanthanide complexes as luminescence probes for VCs.
Alumina supported ruthenium particles with an average diameter of 2 nm were prepared by a modified ethylene glycol reduction method. Catalytic methanation of CO2 over this catalyst was studied by in situ FTIR spectroscopy. After pretreatment in H2, different types of adsorbed species were detected on the catalyst surface at 200 °C. Based on a series of targeted experiments under variation of gas composition, order of addition, reaction time and temperature, a reaction scheme and the rate‐determining steps of CO2 methanation are proposed. Two potential reaction paths for the hydrogenation of CO2 to form CH4 were identified: (I) CO adsorbed on the Ru metal surface acted as active intermediate and the CO methanation followed. The dissociation of CO to form surface carbon represents the rate‐determining step. (II) Formyl species formed by hydrogenation of adsorbed CO2 are the active intermediate and the formation of formyl was the rate‐determining step.
BaTiO3 nanoparticles with extremely high loading are chemically bonded with silicone rubber via “thiol–ene click”, leading to superior dielectric properties.
Summary
Novel microencapsulated phase change materials (MEPCMs) composed of the lead tungstate (PbWO4) shell and paraffin core were designed for shielding of gamma radiation as well as thermal energy storage. Such MEPCMs were prepared via self‐assembly methods and in‐situ precipitation. The PbWO4 shell with excellent photon attenuation can give the resulting MEPCMs an acceptable gamma radiation shielding capability. The chemical composition and structure of microcapsules samples were studied by X‐ray diffractometer (XRD) and Fourier‐transform infrared spectroscopy (FTIR). The effects of different core/shell mass ratios on the surface morphology and microstructure of the MEPCMs were determined by scanning electron microscopy (SEM), energy‐dispersive spectrometer (EDS), and transmission electronic microscopy (TEM). It was confirmed that the microcapsules exhibit a distinct core‐shell structure and a perfect spherical shape. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were used to present thermal stability and thermal‐storage capability of MEPCMs. A high‐purity germanium gamma spectrometer to measure the attenuation coefficient of the microcapsules for gamma rays showed that the MECPMs has good γ‐rays‐shielding property. The multifunction microcapsules in this study have great potential applications for building energy conservation as well as wearable personal protection in nuclear energy engineering.
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