RESUMEN
Ultrathin layers of oxides deposited on atomically flat metal surfaces have been shown to significantly influence the electronic structure of the underlying metal, which in turn alters the catalytic performance. Upscaling of the specifically designed architectures as required for technical utilization of the effect has yet not been achieved. Here, we apply liquid crystalline phases of fluorohectorite nanosheets to fabricate such architectures in bulk. Synthetic sodium fluorohectorite, a layered silicate, when immersed into water spontaneously and repulsively swells to produce nematic suspensions of individual negatively charged nanosheets separated to more than 60â nm, while retaining parallel orientation. Into these galleries oppositely charged palladium nanoparticles were intercalated whereupon the galleries collapse. Individual and separated Pd nanoparticles were thus captured and sandwiched between nanosheets. As suggested by the model systems, the resulting catalyst performed better in the oxidation of carbon monoxide than the same Pd nanoparticles supported on external surfaces of hectorite or on a conventional Al2 O3 support. XPS confirmed a shift of Pd 3d electrons to higher energies upon coverage of Pd nanoparticles with nanosheets to which we attribute the improved catalytic performance. DFT calculations showed increasing positive charge on Pd weakened CO adsorption and this way damped CO poisoning.
RESUMEN
Infrared nonlinear optical (IR NLO) crystals are the major materials to widen the output range of solid-state lasers to mid- or far-infrared regions. The IR NLO crystals used in the middle IR region are still inadequate for high-power laser applications because of deleterious thermal effects (lensing and expansion), low laser-induced damage threshold, and two-photon absorption. Herein, the unbiased global minimum search method was used for the first time to search for IR NLO optical materials and ultimately found a new IR NLO material NaGaS2. It meets the stringent demands for IR NLO materials pumped by high-power laser with the highest thermal conductivity among common IR NLO materials able to avoid two-photon absorption, a classic nonlinear coefficient, and wide infrared transparency.
RESUMEN
As important materials in modulating the polarization of light, birefringent crystals have attracted considerable attention and played crucial roles in the field of optical communication and the laser industry. Limited by the transparency range, few birefringent crystals can be used in the deep-ultraviolet (DUV) region, except for α-BaB2O4 (α-BBO). However, the application of α-BBO in the DUV range is restricted by the relatively high cutoff edge and low transmittance rate below 200 nm. In this paper, we design and synthesize a new fluoroborate, Na2B6O9F2, by introducing fluorine into borate system. It possesses a short cutoff edge of 169 nm and birefringence larger than 0.080 at 589.3 nm. The Na2B6O9F2 crystals with sizes up to 3.0 mm × 1.5 mm × 0.2 mm have been grown with good quality by a high-temperature solution method in the open system. First-principles calculations were carried out to understand the optical properties.
RESUMEN
Substitution is an effective method to create new nonlinear optical (NLO) materials with an enhanced second harmonic generation (SHG) response. However, the large SHG enhancement caused by the substitution of Mg2+ for Zn2+ in an isostructural system is rare and has not been investigated yet. Here we elucidate the contribution of Zn2+ with d10 electronic configuration to the SHG response based on two isostructural silicates Sr2MSi2O7 (M = Zn and Mg). The powder SHG measurements show that the SHG response of Sr2ZnSi2O7 is approximately 35 times that of α-SiO2 and 7 times higher than its isostructural compound Sr2MgSi2O7. The calculated band structures reveal that the difference in band gaps is minute and the sp hybridization between 4s-orbitals of Zn and 2p-orbitals of O is stronger than that between 3s-orbitals of Mg and 2p-orbitals of O. The significantly enhanced SHG response of Sr2ZnSi2O7 can be interpreted by the enhanced inter-band dipole resulting from strong sp hybridization between Zn and O. This provides a route to design new materials with enhanced NLO properties in the isostructural system.
RESUMEN
Two non-centrosymmetric metal chalcogenides, BaCdSnS4 and Ba3CdSn2S8, were synthesized using a high temperature solid-state reaction in an evacuated silica tube. Although the two compounds have the same building units in their structures, namely CdS4, SnS4 and BaS8 units, both of them have different structures. BaCdSnS4 crystallizes in the orthorhombic space group Fdd2 and its structure can be characterized by the two-dimensional ∞[Cd-Sn-S] layers composed of corner- and edge-sharing CdS4 and SnS4 tetrahedra with Ba atoms located between the two adjacent ∞[Cd-Sn-S] layers. Ba3CdSn2S8 crystallizes in the space group I4[combining macron]3d of the orthorhombic system and the CdS4 and SnS4 groups are connected with each other via corner-sharing to form a three-dimensional framework, which is different from the 2D ∞[Cd-Sn-S] layer structure in BaCdSnS4. The UV-vis-NIR diffuse-reflectance spectra show that the experimental band gaps are about 2.30 eV for BaCdSnS4 and 2.75 eV for Ba3CdSn2S8, respectively. IR and Raman measurement results indicate that their transparent ranges are up to 25 µm. Second-order NLO measurements show that BaCdSnS4 exhibits strong powder second-harmonic generation (SHG) intensities at 2.09 µm laser pumping that are â¼5 and 0.7 times that of AgGaS2 in the particle size 38-55 and 150-200 µm, respectively, whereas Ba3CdSn2S8 only exhibits SHG intensities of about 0.8 and 0.1 times that of AgGaS2 at the same particle sizes. The origin of the NLO response in BaCdSnS4 may originate from the macroscopic arrangement of the SnS4 and CdS4 tetrahedra. Furthermore, the photoluminescence properties of the two compounds have also been investigated and show obvious blue and green light emission.