Tetrabutylammonium Salts of Aluminum(III) and Gallium(III) Phthalocyanine Radical Anions Bonded with Fluoren‐9‐olato− Anions and Indium(III) Phthalocyanine Bromide Radical Anions

Reduction of aluminum(III), gallium(III), and indium(III) phthalocyanine chlorides by sodium fluorenone ketyl in the presence of tetrabutylammonium cations yielded crystalline salts of the type (Bu₄N⁺)₂[M^III(HFl−O⁻)(Pc^.3−)]^.−(Br⁻) ⋅ 1.5 C₆H₄Cl₂ [M=Al ( 1 ), Ga ( 2 ); HFl−O⁻=fluoren‐9‐olato⁻ anion; Pc=phthalocyanine] and (Bu₄N⁺) [In^IIIBr(Pc^.3−)]^.− ⋅ 0.875 C₆H₄Cl₂ ⋅ 0.125 C₆H₁₄ ( 3 ). The salts were found to contain Pc^.3− radical anions with negatively charged phthalocyanine macrocycles, as evidenced by the presence of intense bands of Pc^.3− in the near‐IR region and a noticeable blueshift in both the Q and Soret bands of phthalocyanine. The metal(III) atoms coordinate HFl−O⁻ anions in 1 and 2 with short Al−O and Ga−O bond lengths of 1.749(2) and 1.836(6) Å, respectively. The C−O bonds [1.402(3) and 1.391(11) Å in 1 and 2 , respectively] in the HFl−O⁻ anions are longer than the same bond in the fluorenone ketyl (1.27–1.31 Å). Salts 1 – 3 show effective magnetic moments of 1.72, 1.66, and 1.79 μ_B at 300 K, respectively, owing to the presence of unpaired S= 1/2 spins on Pc^.3−. These spins are coupled antiferromagnetically with Weiss temperatures of −22, −14, and −30 K for 1 – 3 , respectively. Coupling can occur in the corrugated two‐dimensional phthalocyanine layers of 1 and 2 with an exchange interaction of J /k _B=−0.9 and −1.1 K, respectively, and in the π‐stacking {[In^IIIBr(Pc^.3−)]^.−}₂ dimers of 3 with an exchange interaction of J /k _B=−10.8 K. The salts show intense electron paramagnetic resonance (EPR) signals attributed to Pc^.3−. It was found that increasing the size of the central metal atom strongly broadened these EPR signals.     

含镍WP/MCM-41催化剂二苯并噻吩加氢脱硫性能

以MCM-41为载体,以镍（Ni）为助剂,制备了Ni含量不同的WP/MCM-41催化剂。采用XRD、BET、SEM和XPS对催化剂进行了表征;以二苯并噻吩（DBT）为模型化合物,通过高压微反装置考察催化剂的加氢脱硫（HDS）活性。结果表明,Ni的加入促进了活性组分WP的生长并使其晶相尺寸略有增加,一定含量的Ni有利于提高催化剂的比表面积。Ni对WP/MCM-41催化剂二苯并噻吩HDS反应具有促进作用。少量Ni的加入有利于WP活性相的生成并增加了活性位的数量;加入过量的Ni,在催化剂中形成了具有一定活性的类似Ni-W-P结构的物种,减少了活性组分WP所占的比例,从而使催化剂DBT的 HDS活性降低。其中,Ni的质量分数为1%的催化剂（cat-Ni-1）具有相对较高活性,其DBT 脱硫率和转化率分别为76.78%和72.16%,比不加Ni的催化剂分别提高了30.04%和21.62%。二苯并噻吩在WP/MCM-41催化剂上以加氢脱硫途径为主,Ni的加入对提高加氢脱硫途径选择性起到了促进作用,且加氢脱硫选择性随Ni含量的增加而提高。     

Synthesis of Ni2P promoted trimetallic NiMoW/γ-Al2O3 catalysts for diesel oil hydrotreatment

The Ni2P promoted and γ-Al2O3 supported NiMoW sulfide catalyst consisting of 4 wt% Mo, 22 wt% W, 2 wt% Ni and 2.5 wt% Ni2P was synthesized by a co-impregnation method. The catalysts were characterized by N2 adsorption-desorption, X-ray diffraction (XRD), diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, NH3 temperature-programmed desorption (NH3-TPD) and transmission electron microscopy (TEM). The results showed that Ni2P, Ni, Mo and W species were highly dispersed over γ-Al2O3. The hydrodesulfurization (HDS) of dibenzothiophene (DBT) showed that the presence of Ni2P brought a strong promotional effect on the HDS activity, which was further confirmed by the HDS and hydrodenitrogenation (HDN) of diesel oil under industrial conditions. The enhancement in HDN activity and stability by Ni2P addition could be attributed more to the effect of new active sites of Ni2P than that of acidity modification. The as-prepared Ni2P-NiMoW/γ-Al2O3 catalyst showed better hydrotreating performance than NiMoW/γ-Al2O3 and commercial catalysts.     

Investigation of semi-insulating oxygen-doped GaAs

We found Oxygen-doped GaAs crystals to be suitable materials for CO₂ laser optical component preparation, with application at 10.6 μm. An optical transmission of 55% in the IR spectrum range, between 2 and 15 μm has been reached for such a GaAs type material. The GaAs crystals that we have analysed were grown by two procedures: Horizontal Bridgman (HB) and Liquid Encapsulated Czochralski (LEC). The HB method has been used for obtaining pure (undoped) crystals, while the oxygen-doped GaAs ingots were grown by LEC technique. The two types of samples processed in the same manner as regards mechanical polishing and chemical etching, which were investigated by Hall measurements, optical transmission spectrometry and elastic recoil detection analysis (ERDA) technique. The GaAs:O (LEC) has near semi-insulating properties as can be observed from the results of the electrical resistivity and Hall effect measurements. The ERDA spectrum shows an intense signal of oxygen in the bulk of GaAs:O (LEC) crystals, while the oxygen signal is not present in the ERDA spectrum of the undoped GaAs (HB). We consider that these results could recommend the ERDA technique as a possible qualitative and quantitative analysis in an ion-beam accelerator for oxygen content in oxygen-doped GaAs crystals. The analysis is not sensitive to the native oxide, as could be seen by measuring GaAs (HB) undoped crystals.     

Crystallographic report: [1,3‐Di(mestityl)imidazol‐2‐ylidene]gallium iodide dihydride

The structure of the N‐heterocyclic gallium hydride complex, [GaH₂I{CN(Mes)C₂H₂N(Mes)}], Mes = mesityl, shows both hydride ligands to be bonded to the distorted tetrahedral gallium centre. Copyright © 2003 John Wiley & Sons, Ltd.     

Two Beam Coupling in Semi-Insulating GaN Film Using Electroabsorption Effect

The photorefractive effect was observed in He-ion-implanted semi-insulating GaN film in the UV spectral region. The photorefractive grating is induced by the electroabsorption effect near the band-edge. Two beam coupling experiments were performed at a wavelength of 363.8 nm. The experimental results indicate that absorption grating mainly contributes to the beam coupling.     

Photoluminescence of gallium arsenide electron-irradiated at 20 K

The processes of defect formation in single crystals of gallium arsenide electron-irradiated at cryogenic temperatures (∼20 K) have been investigated by the luminescence method. It is shown that at such temperatures the primary radiation-induced defects, in particular, intrinsic interstitial atoms, can migrate in a crystal and form complexes with their participation. Institute of Solid-State and Semiconductor Physics of the Academy of Sciences of Belarus, 17, P. Brovka St., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 1, pp. 122–124, January–February, 1997.