硅铝催化剂催化有机溶剂木质素的解聚

E cient conversion of lignin to fine chemicals and biofuel become more and more attractive in biorefinery. In this work, we used a series of silica-alumina catalysts (i.e., SiO₂-Al₂O₃, HY, Hβ, and HZSM-5) to degrade lignin into arenes and phenols. The relationship between the catalyst structure and lignin depolymerization performance was investigated. The results showed that both acidity and pore size of the catalyst could in uence the conversion of lignin. In the volatilizable product, phenols were identified as the main phenolic monomers via gas chromatography-mass spectrometer. SiO₂-Al₂O₃ was the most effcient catalyst, giving 90.96% degree of conversion, 12.91% yield of phenols, and 2.41% yield of arenes in ethanol at 280℃ for 4 h. The Fourier transform infrared spectroscopy and ¹H nuclear magnetic resonance spectroscopy analysis demonstrated that deoxygenation and alkylation occurred in this process. The effect of solvents was also investigated and the results showed that ethanol was the most effcient solvent.     

HIGH-YIELD PRODUCTION OF MULTI-WALLED CARBON NANOTUBES BY CATALYTIC DECOMPOSITION OF BENZENE VAPOR

Multi-walled carbon nanotubes (CNTs) have been synthesized on γ-Al₂O₃ supported unitary, binary or trinity metal (Fe, Co, Ni) catalysts with benzene as carbon source in the range of 600 to 810 ℃. The growth of CNTs was carried out in a fixed bed flow reactor and the quality of carbon deposits was characterized by transmission electron microscopy. The preparation was optimized and the high-yield production of CNTs has been achieved for three mixture catalysts with the yield of high-quality CNTs higher than 200% within 60 min, reaching a maximum of 278% for 1.51 mmol/g Fe-1.51 mmol/g Co/γ-Al₂O₃ catalyst. This provides a good alternative for future large scale and low cost production of CNTs for applications.     

活性炭负载Pt/Fe3O4催化剂及其选择性转移加氢肉桂醛的催化性能

A variety of spherical and structured activated charcoal supported Pt/Fe₃O₄ composites with an average particle size of ～100 nm have been synthesized by a self-assembly method using the difference of reduction potential between Pt (IV) and Fe (Ⅱ) precursors as driving force. The formed Fe₃O₄ nanoparticles (NPs) effectively prevent the aggregation of Pt nanocrystallites and promote the dispersion of Pt NPs on the surface of catalyst, which will be favorable for the exposure of Pt active sites for high-efficient adsorption and contact of substrate and hydrogen donor. The electron-enrichment state of Pt NPs donated by Fe₃O₄ nanocrystallites is corroborated by XPS measurement, which is responsible for promoting and activating the terminal C=O bond of adsorbed substrate via a vertical configuration. The experimental results show that the activated charcoal supported Pt/Fe₃O₄ catalyst exhibits 94.8% selectivity towards cinnamyl alcohol by the transfer hydrogenation of cinnamaldehyde with Pt loading of 2.46% under the optimum conditions of 120℃ for 6 h, and 2-propanol as a hydrogen donor. Additionally, the present study demonstrates that a high-efficient and recyclable catalyst can be rapidly separated from the mixture due to its natural magnetism upon the application of magnetic field.     

Development and characteristic analysis of a field-plated Al2O3/AlInN/GaN MOS–HEMT

We present an AlInN/AlN/GaN MOS–HEMT with a 3 nm ultra-thin atomic layer deposition (ALD) Al₂O₃ dielectric layer and a 0.3 μm field-plate (FP)-MOS--HEMT. Compared with a conventional AlInN/AlN/GaN HEMT (HEMT) with the same dimensions, a FP-MOS--HEMT with a 0.6 μm gate length exhibits an improved maximum drain current of 1141 mA/mm, an improved peak extrinsic transconductance of 325 mS/mm and effective suppression of gate leakage in both the reverse direction (by about one order of magnitude) and the forward direction (by more than two orders of magnitude). Moreover, the peak extrinsic transconductance of the FP-MOS--HEMT is slightly larger than that of the HEMT, indicating an exciting improvement of transconductance performance. The sharp transition from depletion to accumulation in the capacitance--voltage (C--V) curve of the FP-MOS--HEMT demonstrates a high-quality interface of Al₂O₃/AlInN. In addition, a large off-state breakdown voltage of 133 V, a high field-plate efficiency of 170 V/μ m and a negligible double-pulse current collapse is achieved in the FP-MOS--HEMT. This is attributed to the adoption of an ultra-thin Al₂O₃ gate dielectric and also of a field-plate on the dielectric of an appropriate thickness. The results show a great potential application of the ultra-thin ALD-Al₂O₃ FP-MOS--HEMT to deliver high currents and power densities in high power microwave technologies.     

活化气氛对钼基合成醇催化剂的结构和性能的影响

Activated carbon supported Mo-based catalysts were prepared and reduced under different activation atmospheres, including pure H₂, syngas (H₂/CO=2/1), and pure CO. The catalysts structures were characterized by X-ray diffraction, X-ray absorption fine structure, and in situ diffuse reflectance infrared Fourier transform spectroscopy. The catalytic performance for the higher alcohol synthesis from syngas was tested. The pure H₂ treatment showed a high reduction capacity. The presence of a large amount of metallic Co⁰. and low valence state Mo^φ+ (0<φ<2) on the surface suggested a super activity for the CO dissociation and hydrogenation, which promoted hydrocarbons formation and reduced the alcohol selectivity. In contrast, the pure CO-reduced catalyst had a low reduction degree. The Mo and Co species at the catalyst mainly existed in the form of Mo⁴⁺ and Co²⁺. The syngas-reduced catalyst showed the highest activity and selectivity for the higher alcohols synthesis. We suggest that the syngas treatment had an appropriate reduction capacity that is between those of pure H₂ and pure CO and led to the coexistence of multivalent Co species as well as the enrichment of Mo^δ+ on the catalyst''s surface. The synergistic effects between these active species provided a better cooperativity and equilibrium between the CO dissociation, hydrogenation and CO insertion and thus contributed beneficially to the formation of higher alcohols.     

Relation between oxidation microstructure and the maximum energy product loss of a Sm2Co17 magnet oxidized at 500 ℃

The oxidation microstructure and maximum energy product (BH)_max loss of a Sm(Co_0.76, Fe_0.1, Cu_0.1, Zr_0.04)₇ magnet oxidized at 500 ℃ were systematically investigated. Three different oxidation regions were formed in the oxidized magnet: a continuous external oxide scale, an internal reaction layer, and a diffusion zone. Both room-temperature and high-temperature (BH)_max losses exhibited the same parabolic increase with oxidation time. An oxygen diffusion model was proposed to simulate the dependence of (BH)_max loss on oxidation time. It is found that the external oxide scale has little effect on the (BH)_max loss, and both the internal reaction layer and diffusion zone result in the (BH)_max loss. Moreover, the diffusion zone leads to more (BH)_max loss than the internal reaction layer. The values of the oxidation rate constant k for internal reaction layer and oxygen diffusion coefficient D for diffusion zone were obtained, which are about 1.91 × 10^-10 cm²/s and 6.54 × 10^-11 cm²/s, respectively.     

窄带隙KNb1-xFexO3-δ的室温铁磁性

We have investigated the structure, optical and magnetic properties of ferroelectric KNb_1-xFexO_3-δ (X=0, 0.01, 0.03, 0.05, 0.10, 0.15, 0.20, 0.25) synthesized by a traditional solid-state reaction method. According to the X-ray diffraction and the results of Rietveld refinement, all the samples maintain orthorhombic distorted perovskite structures with Amm2 space group without any secondary phase, suggesting the well incorporation of Fe ions into the KNbO₃ matrix. With the increase of Fe concentration, the band gap of each sample is decreased gradually, which is much smaller than the 3.18 eV band gap of pure KNbO₃. Through X-ray photoelectron spectrum analysis, the increased density of oxygen vacancy and Fe ions may be responsible for the observed decrease in band gap. Compared with the pure KNbO₃, Fe doped samples exhibit room-temperature weak ferromagnetism. The ferromagnetism in KNb_1-xFexO_3-δ with low-concentration dopants (X=0.01-0.10) can be attributed to the bound magnetic polaron mediated exchange. The enhancement of magnetism for the high-concentration (X=0.10-0.20) doped samples may arise from the further increase of magnetic Fe ions.     

纯Cr2O3包覆Li4Ti5O12微球的制备及其储锂性能研究

The pure Cr₂O₃ coated Li₄Ti₅O₁₂ microspheres were prepared by a facile and cheap solutionbased method with basic chromium(III) nitrate solution (pH=11.9). And their Li-storage properties were investigated as anode materials for lithium rechargeable batteries. The pure Cr₂O₃ works as an adhesive interface to strengthen the connections between Li₄Ti₅O₁₂ particles, providing more electric conduction channels, and reduce the inter-particle resistance. Moreover, LixCr₂O₃, formed by the lithiation of Cr₂O₃, can further stabilize Li₇Ti₅O₁₂ with high electric conductivity on the surface of particles. While in the acid chromium solution (pH=3.2) modification, besides Cr₂O₃, Li₂CrO₄ and TiO₂ phases were also found in the final product. Li₂CrO₄ is toxic and the presence of TiO₂ is not welcome to improve the electrochemical performance of Li₄Ti₅O₁₂ microspheres. The reversible capacity of 1% Cr₂O₃-coated sample with the basic chromium solution modification was 180 mAh/g at 0.1 C, and 134 mAh/g at 10 C. Moreover, it was even as high as 127 mAh/g at 5 C after 600 cycles. At-20℃, its reversible specific capacity was still as high as 118 mAh/g.     

Reactions at the interface La0.5Ca0.5MnO3-YSZ/Al2O3 under anodic current

The reaction at the interface of a solid electrolyte cell between air electrode (La_0.5Ca_0.5MnO₃) and YSZ-electrolyte with different Al₂O₃-contents was investigated by electron microscopy (SEM) and x-ray diffraction (XRD). Formation of MnAl₂O₄ was detected in a 5 μm diffusion zone within the electrolyte. MnAl₂O₄ formation can be explained by diffusion of Mn-ions into the electrolyte and subsequent reaction with the α-Al₂O₃ grains during sintering. Cell performance and long-term stability in SOFC operation are not negatively affected by MnAl₂O₄ formation. However a rise in electrode resistance and slow delamination of perovskite oxide electrode were observed after some hours of electrolysis. This reaction is the consequence of oxygen gas pressure at the electrolyte in the MnAl₂O₄ diffusion zone. It is caused by local increase of electronic conductivity by MnAl₂O₄ formation. Long-term stability also for electrolysis conditions has been achieved by an additional intermediate YSZ-layer between air electrode and electrolyte. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

利用原位傅里叶变换红外光谱诊断催化剂的特性和催化活性

The present work establishes a systematic approach based on the application of in-situ Fourier transform infrared spectroscopy (FTIR) for the investigation of the crystal structure, thermal stability, redox behavior (temperature-programmed reduction/temperatureprogrammed re-oxidation) as well as the catalytic properties of Co₃O₄ thin films. The syntheses of Co₃O₄ were achieved by chemical vapor deposition in the temperature range of 400-500℃. The structure analysis of the as-prepared material revealed the presence of two prominent IR bands peaking at 544 cm^-1 (υ₁) and 650 cm^-1 (υ₂) respectively, which originate from the stretching vibrations of the Co-O bond, characteristic of the Co₃O₄ spinel. The lattice stability limit of Co₃O₄ was estimated to be above 650℃. The redox properties of the spinel structure were determined by integrating the area under the emission bands υ₁ and υ₂ as a function of the temperature. Moreover, Co₃O₄ has been successfully tested as a catalyst towards complete oxidation of dimethyl ether below 340 ℃. The exhaust gas analysis during the catalytic process by in situ absorption FTIR revealed that only CO₂ and H₂O were detected as the final products in the catalytic reaction. The redox behavior suggests that the oxidation of dimethyl ether over Co₃O₄ follows a Mars-van Krevelen type mechanism. The comprehensive application of in situ FTIR provides a novel diagnostic tool in characterization and performance test of catalysts.