BIS(DIAZASILAPHOSPHETIDINES) AND THEIR METAL COMPLEXES

The syntheses and solid-state structures of bis(diazasilaphosphetidines) of the type [Me ₂ Si(μ-N ^t Bu) ₂ P] ₂ NR, R = Ph, ⁱ Pr, ^t Bu, of the P-chiral analogue [Me ₂ Si(μ-N ^t Bu)(μ-N-2,6- ⁱ PrPh)P] ₂ (C ₂ H ₄ ), and of some of their metal complexes are reported. The highly electron-rich, modular bis(phosphines) are easy to synthesize and may have applications in catalysis.     

Decomposition of P2S2N4(Si(CH3)3)4A12C14 as Studied by FT-Raman and Quantum Chemistry Means

The dimeric title compound decomposes upon heating to give the monomer and desulphurized monomer as shown by FT-Raman and quantum chemical means.     

Hydrolysis-Condensation Kinetics of Different Silane Coupling Agents

Abstract

The hydrolysis kinetics of 14 alkoxy silane coupling agents were carried out in an ethanol:water 80:20 (w/w) solution under acidic conditions and were monitored by ¹H, ¹³C, and ²⁹Si NMR spectroscopy. Acidic conditions were selected in order to enhance the silanol formation and to slow down the self-condensation between the resulting hydrolysed silanol groups. In situ ²⁹Si NMR spectroscopy allowed the determination of the intermediate species as a function of the reaction time. Thus, the following silane coupling agents were studied: 3-methacryloxypropyl trimethoxy silane (MPMS), 3-mercaptopropyl trimethoxy silane (MRPMS), 3-cyanopropyl triethoxy silane (CPES), triethoxy vinyl silane (VES), trimethoxy (2-phenylethyl) silane (PEMS), octyl triethoxy silane (OES), trimethoxy (7-octen-1-yl) silane (OEMS), 3-aminopropyl triethoxy silane (APES), 3-aminopropyl trimethoxy silane (APMS), 3-(2-aminoethylamino)propyl trimethoxy silane, (DAMS), 3-[2-(2-aminoethylamino)-ethylamino]propyl trimethoxy silane (TAMS), 4-amino-3,3-dibutyl trimethoxy silane (ADBMS), trimethoxy [3-(phenylamino)propyl] silane (PAPMS), and triethoxy-3-(2-imidazolin-1-yl) propyl silane (IZPES). A parameter quantifying the grafting potentiality of each silane coupling agent towards OH-rich solid substrates (such as cellulose) was established as a function of the nature of the alkoxy groups (methoxy or ethoxy), as well as that of the fourth substituent (vinyl, aminopropyl, etc.) of the silane studied.

GRAPHICAL ABSTRACT     

A Direct and Rapid Route to Synthesize Pd/Si‐MCM‐41 at Room Temperature

The pure silica mesoporous molecular sieve MCM‐41 was synthesized under hydrothermal conditions. Pd/Si‐MCM‐41 was prepared by the incipient wetness impregnation of pure silica MCM‐41 with mixed solution of PdCl₂, ethanol and CH₂Cl₂. The samples were characterized by x‐ray diffraction (XRD), transmission electron microscopy (TEM), and nitrogen adsorption–desorption isotherms at 77 K. The XRD and TEM results reveal that Pd is actually anchored inside the pores of Si‐MCM‐41 and the Si‐MCM‐41 structure is clearly maintained after impregnation.     

碱液后处理对纳米ZSM-5沸石孔道和酸度的影响

采用XRD、N2物理吸附、NH3-TPD以及TEM、IR和NMR手段,系统研究了NaOH碱液后处理对低硅铝比纳米ZSM-5沸石(Si/Al摩尔比为14.5、晶粒度为20～50 nm)孔道和酸度的影响.结果表明,在碱液中,低硅铝比纳米ZSM-5沸石主要发生限域脱硅,而且低硅铝比纳米ZSM-5沸石的碱液脱硅难度大于高硅铝比沸石.但在适当的碱液处理条件下(碱硅比为0.19～0.35,温度为60～80℃,处理时间为2～5 h)可以在其晶体内产生大量介孔,增加比表面积和孔容;同时增加弱酸和中强酸的浓度,并提高L酸比例.L酸的大量增加主要是由于产生了裸露的骨架铝(≡Alδ+),这与文献的观点有所不同.     

Raman spectroscopy of CaM2+Ge2O6 (M2+ = Mg,Mn, Fe,Co, Ni,Zn) clinopyroxenes

The Raman spectra of Ge‐clinopyroxenes CaM²⁺Ge₂O₆ (M²⁺ = Mg, Mn, Fe, Co, Ni, Zn), general formula M2M1T₂O₆, are reported for the first time. Their spectral features are discussed in comparison with corresponding Si‐pyroxenes. The vibrational wavenumbers of germanates may be roughly obtained by a scale factor of about ~0.8 by those of the corresponding silicates, due to the Ge‐Si mass difference. The main peaks in the germanate Raman spectra at ~850 and ~540 cm⁻¹ may be related to Ge‐O tetrahedral stretching and chain bending, respectively; minor peaks between 200 and 400 cm⁻¹ are ascribed to bending and stretching of the non‐tetrahedral cations. Within Ge‐pyroxenes, possible correlations between crystallographic parameters and the vibrational wavenumbers are investigated. The main stretching mode at ~850 cm⁻¹ shows wavenumber changes with M²⁺ substitutions, but no simple correlation can be found with M²⁺ cation mass or size. On the other hand, the chain bending wavenumber linearly decreases with increasing ionic radius of the M²⁺ cation: the expansion of the M1 polyhedron reduces the chain kinking angle and the Ge‐Ge distances correspondingly increase. Copyright © 2015 John Wiley & Sons, Ltd.     

Indirectly Detected DNP-Enhanced 17O NMR Spectroscopy: Observation of Non-Protonated Near-Surface Oxygen at Naturally Abundant Silica and Silica-Alumina

Recent studies have shown that dynamic nuclear polarization (DNP) can be used to detect ¹⁷O solid-state NMR spectra of naturally abundant samples within a reasonable experimental time. Observations using indirect DNP, which relies on ¹H mediation in transferring electron hyperpolarization to ¹⁷O, are currently limited mostly to hydroxyls. Direct DNP schemes can hyperpolarize non-protonated oxygen near the radicals; however, they generally offer much lower signal enhancements. In this study, we demonstrate the detection of signals from non-protonated ¹⁷O in materials containing silicon. The sensitivity boost that made the experiment possible originates from three sources: indirect DNP excitation of ²⁹Si via protons, indirect detection of ¹⁷O through ²⁹Si nuclei using two-dimensional ²⁹Si{¹⁷O} D-HMQC, and Carr-Purcell-Meiboom-Gill refocusing of ²⁹Si magnetization during acquisition. This ²⁹Si-detected scheme enabled, for the first time, 2D ¹⁷O−²⁹Si heteronuclear correlation spectroscopy in mesoporous silica and silica-alumina surfaces at natural abundance. In contrast to the silanols showing motion-averaged ¹⁷O signals, the framework oxygens exhibit unperturbed powder patterns as unambiguous fingerprints of surface sites. Along with hydroxyl oxygens, detection of these moieties will help in gaining more atomistic-scale insights into surface chemistry.     

First principles calculation of the opto-electronic properties of (110) growth axis SiGe superlattices

Using two versions of the first principles full potential linear muffin-tin orbitals method (FPLMTO) which enable an accurate treatment of the interstitial regions, the electronic and optical properties of (110) growth axis Si/SiGe superlattices are investigated. A comparative study with (001) growth axis superlattices is made. In particular, it is found that the bottom of the conduction band (CB) is closer to Γ$\Gamma$ in the (110) system but the optical activity is not enhanced. Furthermore, the absorption spectra of the superlattices are calculated and are found to be quite different from those of bulk Si and Ge but fairly close to their average.     

The Rayleigh law in silicon doped hafnium oxide ferroelectric thin films

A wealth of studies have confirmed that the low‐field hysteresis behaviour of ferroelectric bulk ceramics and thin films can be described using Rayleigh relations, and irreversible domain wall motion across the array of pining defects has been commonly accepted as the underlying micro‐mechanism. Recently, HfO₂ thin films incorporated with various dopants were reported to show pronounced ferroelectricity, however, their microscopic domain structure remains unclear till now. In this work, the effects of the applied electric field amplitude, frequency and temperature on the sub‐coercive polarization reversal properties were investigated for 10 nm thick Si‐doped HfO₂ thin films. The applicability of the Rayleigh law to ultra‐thin ferroelectric films was first confirmed, indicating the existence of a multi‐domain structure. Since the grain size is about 20–30 nm, a direct observation of domain walls within the grains is rather challenging and this indirect method is a feasible approach to resolve the domain structure. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)