Studies on basicity of alkali metal catron exchanged β and X zeolites by pyrrole-IR spectroscopy

The strength of basic sites has been measured by pyrrole-IR on alkali metal cation exchanged β and X zeolites, as well as NaOH loaded Naβ. The influence of cation type and the structure of zeolites on their basicity has been studied. The acidic and basic properties of the samples were investigated by NH3-TPD and isopropanol reaction. It was shown that the strength of basic sites on samples could be characterized by the shift of vNH band in the pyrrole-IR spectra. The framework oxygen charges were calculated from the Sanderson electronegativity. The changes in basic properties with various alkali metal cation are consistent with the changes of local oxygen charges of the zeolite framework.     

Quantitative Comparison of REAPDOR and TRAPDOR Experiments by Numerical Simulations and Determination of H–Al Distances in Zeolites

Quantitative H–Al distances in acid sites of two zeolites with MFI and IFR framework topology were obtained by numerical simulation of ¹H{²⁷Al} rotational echo adiabatic passage double resonance (REAPDOR) experiments. A ²⁷Al offset-dependent data set yields for each resolved ¹H NMR line a corresponding nuclear electric quadrupole coupling constant of the neighboring ²⁷Al site. This information is used for analyzing a second data set for on-resonance irradiation, where the dipolar evolution time (number of rotor cycles) was varied, to yield the ¹H–²⁷Al dipolar coupling constant. Numerical simulations indicate that the REAPDOR method does not depend significantly on the polar angles, defining the orientation of the electric field gradient tensor of ²⁷Al with respect to the Al–H dipolar vector. In contrast, the transfer of populations in double resonance sequence is sensitive to these angles, and it can be thus used to measure them.     

Characterisation of the photocatalyst Pilkington Activ™: a reference film photocatalyst?

Pilkington Glass Activ™ represents a possible suitable successor to P25 TiO₂, especially as a benchmark photocatalyst film for comparing other photocatalyst or PSH self-cleaning films. Activ™ is a glass product with a clear, colourless, effectively invisible, photocatalytic coating of titania that also exhibits PSH. Although not as active as a film of P25 TiO₂, Activ™ vastly superior mechanical stability, very reproducible activity and widespread commercial availability makes it highly attractive as a reference photocatalytic film. The photocatalytic and photo-induced superhydrophilitic (PSH) properties of Activ™ are studied in some detail and the results reported. Thus, the kinetics of stearic acid destruction (a 10⁴ electron process) are zero order over the stearic acid range 4–129 monolayers and exhibit formal quantum efficiencies (FQE) of 0.7×10⁻⁵ and 10.2×10⁻⁵ molecules per photon when irradiated with light of 365±20 and 254 nm, respectively; the latter appears also to be the quantum yield for Activ™ at 254 nm. The kinetics of stearic acid destruction exhibit Langmuir–Hinshelwood-like saturation type kinetics as a function of oxygen partial pressure, with no destruction occurring in the absence of oxygen and the rate of destruction appearing the same in air and oxygen atmospheres. Further kinetic work revealed a Langmuir adsorption type constant for oxygen of 0.45±0.16 kPa⁻¹ and an activation energy of 19±1 kJ mol⁻¹. A study of the PSH properties of Activ™ reveals a high water contact angle (67°) before ultra-bandgap irradiation reduced to 0° after prolonged irradiation. The kinetics of PSH are similar to those reported by others for sol–gel films using a low level of UV light. The kinetics of contact angle recovery in the dark appear monophasic and different to the biphasic kinetics reported recently by others for sol–gel films [J. Phys. Chem. B 107 (2003) 1028]. Overall, Activ™ appears a very suitable reference material for semiconductor film photocatalysis.     

Elasticity in nanocrystalline Nd2Fe14B+αFe magnetic composites

The dynamic Young modulus (E) of magnetic Nd₂Fe₁₄B+αFe nanocomposites is investigated with mechanical spectroscopy techniques (vibrating reed configuration, f≈1.5 kHz <10⁻⁶). Reduced values of E are obtained (88–152 GPa) as compared with that predicted by the rule of mixtures for the composite (164 GPa). Three contributions to this reduction are briefly discussed: a large volume fraction of the specimen with grain boundary like structure; internal pores, resulting from the high cooling rate during processing (10⁶ K/min) and magneto-mechanical effects. Even when porosity is identified as the principal cause of modulus reduction, magnetic effects are also detected.     

Temperature dependence of excitonic luminescence from nanocrystalline ZnO films

The properties of the excitonic luminescence for nanocrystalline ZnO thin films are investigated by using the dependence of excitonic photoluminescence (PL) spectra on temperature. The ZnO thin films are prepared by thermal oxidation of ZnS films prepared by low-pressure metalorganic chemical vapor deposition (LP-MOCVD) technique. The X-ray diffraction (XRD) indicates that ZnO thin films have a polycrystalline hexagonal wurtzite structure with a preferred (0 0 2) orientation. A strong ultraviolet (UV) emission peak at 3.26 eV is observed, while the deep-level emission band is barely observable at room temperature. The strength of the exciton-longitudinal-optical (LO) phonon coupling is deduced from the temperature dependence of the full-width at half-maximum (FWHM) of the fundamental excitonic peak, decrease in exciton-longitudinal-optical (LO) phonon coupling strength is due to the quantum confinement effect.     

Strong visible PL from the nc-Si thin film by Ni silicide mediated crystallization

We studied the growth of nanocrystalline silicon (nc-Si) thin film exhibiting a strong room temperature photoluminescence (PL) at 1.81–2.003 eV. The amorphous silicon was crystallized by Ni silicide mediated crystallization (Ni SMC) and then Secco-etched to exhibit the PL. The PL peak energy and intensity increase with increasing the metal density on the a-Si because of the reduction in the grain size down to 2 nm. The photoluminescence energy and peak intensity depend strongly on the Secco etch time because the grain size is reduced by etching the grain boundaries.     

在H－ZSM－5沸石上甲醇转化为汽油的初始产物分布

在Ｈ－ＺＳＭ－５沸石上甲醇转化为汽油的初始产物分布姜玄珍（浙江大学化学系，杭州３１００２７）Ｒ．Ｆ．Ｈｏｗｅ（新南威尔士大学物理化学系，澳大利亚）关键词Ｈ－ＺＳＭ－５沸石，甲醇转化汽油，产物分布以氢型ＺＳＭ－５沸石作催化剂转化甲醇为汽油（ＭＴＧ），在...