Homogeneous pinhole free 1 nm Al2O3 tunnel barriers on graphene

We report on the topographical and electrical characterisations of 1 nm thick Al2O3 dielectric films on graphene. The Al 2O3 is grown by sputtering a 0.6 nm Al layer on graphene and subsequentially oxidizing it in an O2 atmosphere. The Al 2O3 layer presents no pinholes and is homogeneous enough to act as a tunnel barrier. A resistance-area product in the mega-ohm micrometer-square range is found. Comparatively, the growth of Al 2O3 by evaporation does not lead to well-wetted films on graphene. Application of this high quality sputtered tunnel barrier to efficient spin injection in graphene is discussed. © 2012 American Institute of Physics.

Nitrogen defects and ferromagnetism in Cr-doped dilute magnetic semiconductor AlN from first principles

High Curie temperature of 900 K has been reported in Cr-doped AlN diluted magnetic semiconductors prepared by various methods, which is exciting for spintronic applications. It is believed that N defects play important roles in achieving the high-temperature ferromagnetism in good samples. Motivated by these experimental advances, we use a full-potential density-functional-theory method and supercell approach to investigate N defects and their effects on ferromagnetism of (Al,Cr)N with N vacancies (V-N). We investigate the structural and electronic properties of V-N, single Cr atom, Cr-Cr atom pairs, Cr-V-N pairs, and so on. In each case, the most stable structure is obtained by comparing different atomic configurations optimized in terms of the total energy and the force on every atom, and then it is used to calculate the defect formation energy and study the electronic structures. Our total-energy calculations show that the nearest substitutional Cr-Cr pair with the two spins in parallel is the most favorable and the nearest Cr-V-N pair makes a stable complex. Our formation energies indicate that V-N regions can be formed spontaneously under N-poor condition because the minimal V-N formation energy equals -0.23 eV or Cr-doped regions with high enough concentrations can be formed under N-rich condition because the Cr formation energy equals 0.04 eV, and hence real Cr-doped AlN samples are formed by forming some Cr-doped regions and separated V-N regions and through subsequent atomic relaxation during annealing. Both of the single Cr atom and the N vacancy create filled electronic states in the semiconductor gap of AlN. N vacancies enhance the ferromagnetism by adding mu(B) to the Cr moment each but reduce the ferromagnetic exchange constants between the spins in the nearest Cr-Cr pairs. These calculated results are in agreement with experimental observations and facts of real Cr-doped AlN samples and their synthesis. Our first-principles results are useful to elucidate the mechanism for the ferromagnetism and to explore high-performance Cr-doped AlN diluted magnetic semiconductors.

Enhanced Pockels effect in GaN/AlxGa1-xN superlattice measured by polarization-maintaining fiber Mach-Zehnder interferometer

Six-period 4 nm GaN/10 nm AlxGa1-xN superlattices with different Al mole fractions x were prepared on (0001) sapphire substrates by low-temperature metal-organic chemical vapor deposition. The linear electro-optic (Pockels) effect was studied by a polarization-maintaining fiber-optical Mach-Zehnder interferometer system with an incident light wavelength of 1.55 mu m. The measured electro-optic coefficients, gamma(13)=5.60 +/- 0.18 pm/V, gamma(33)=19.24 +/- 1.21 pm/V (for sample 1, x=0.3), and gamma(13)=3.09 +/- 0.48 pm/V, gamma(33)=8.94 +/- 0.36 pm/V (for sample 2, x=0.1), respectively, are about ten times larger than those of GaN bulk material. The enhancement effect in GaN/AlxGa1-xN superlattice can be attributed to the large built-in field at the interfaces, depending on the mole fraction of Al. (C) 2007 American Institute of Physics.

Chemical composition and elastic strain in AlInGaN quaternary films

High-quality AlInGaN quaternary layers were grown on c-Al2O3 using a thick GaN template. A full width at half maximum of 0.075 degrees from AlInGaN(0004) rocking curve and a minimum yield of 5.6% from Rutherford backscattering/channelling spectrometry (RBS) prove the AlInGaN layer of a comparable crystalline quality with GaN layers. The chemical compositions (both of Al and In contents) of AlInGaN layers are directly obtained from RBS and elastic recoil detection analysis. The lattice parameters both in perpendicular and parallel directions are deduced from X-ray diffraction. The AlInGaN layer is found to process a compressive strain in parallel direction and a tensile strain in perpendicular direction. (c) 2006 Elsevier B.V. All rights reserved.

In-Situ Boron and Aluminum Doping and Their Memory Effects in 4H-SiC Homoepitaxial Layers Grown by Hot-Wall LPCVD

The in-situ p-type doping of 4H-SiC grown on off-oriented (0001) 4H-SiC substrates was performed with trimethylaluminum (TMA) and/or diborane (B2H6) as the dopants. The incorporations of Al and B atoms and their memory effects and the electrical properties of p-type 4H-SiC epilayers were characterized by secondary ion mass spectroscopy (SIMS) and Hall effect measurements, respectively. Both Al- and B-doped 4H-SiC epilayers were p-type conduction. It was shown that the profiles of the incorporated boron and aluminum concentration were in agreement with the designed TMA and B2H6 flow rate diagrams. The maximum hole concentration for the Al doped 4H-SiC was 3.52x10(20) cm(-3) with Hall mobility of about 1 cm(2)/Vs and resistivity of 1.6 similar to 2.2x10(-2) Omega cm. The heavily boron-doped 4H-SiC samples were also obtained with B2H6 gas flow rate of 5 sccm, yielding values of 0.328 Omega cm for resistivity, 5.3x10(18) cm(-3) for hole carrier concentration, and 7 cm(2)/VS for hole mobility. The doping efficiency of Al in SiC is larger than that of B. The memory effects of Al and B were investigated in undoped 4H-SiC by using SIMS measurement after a few run of doped 4H-SiC growth. It was clearly shown that the memory effect of Al is stronger than that of B. It is suggested that p-type 4H-SiC growth should be carried out in a separate reactor, especially for Al doping, in order to avoid the join contamination on the subsequent n-type growth. 4H-SiC PiN diodes were fabricated by using heavily B doped epilayers. Preliminary results of PiN diodes with blocking voltage of 300 V and forward voltage drop of 3.0 V were obtained.

夏玉米低定额畦灌田间试验研究

为了合理利用水资源,探索实现低定额均匀灌溉的适宜方法和技术路线,设计作物高效用水的有限灌溉制度,在陕西省杨凌区中壤土玉米地开展了不同畦田规格和灌水定额对土壤水分及玉米产量影响的田间试验。结果表明:对于田面坡度一定的试验田块,入畦单宽流量在3～6lm/s范围内,畦田宽度在4m以内时,各处理小区的土壤平均含水量无显著性差异,但畦田内土壤水分分布却有不同差异,当畦宽2～3m,畦长50m时可达到较高灌水效率(Ea>80%)和灌水均匀度(DU>80%);玉米拔节-抽雄期的灌水定额处理对玉米的生长存在明显影响;不同灌水定额对作物产量、水分利用效率影响显著。

Ab initio calculations for the neutral and charged O vacancy in sapphire

The energetics, lattice relaxation, and the defect-induced states of st single O vacancy in alpha-Al2O3 are studied by means of supercell total-energy calculations using a first-principles method based on density-functional theory. The supercell model with 120 atoms in a hexagonal lattice is sufficiently large to give realistic results for an isolated single vacancy (square). Self-consistent calculations are performed for each assumed configuration of lattice relaxation involving the nearest-neighbor Al atoms and the next-nearest-neighbor O atoms of the vacancy site. Total-energy data thus accumulated are used to construct an energy hypersurface. A theoretical zero-temperature vacancy formation energy of 5.83 eV is obtained. Our results show a large relaxation of Al (O) atoms away from the vacancy site by about 16% (8%) of the original Al-square (O-square) distances. The relaxation of the neighboring Al atoms has a much weaker energy dependence than the O atoms. The O vacancy introduces a deep and doubly occupied defect level, or an F center in the gap, and three unoccupied defect levels near the conduction band edge, the positions of the latter are sensitive to the degree of relaxation. The defect state wave functions are found to be not so localized, but extend up to the boundary of the supercell. Defect-induced levels are also found in the valence-band region below the O 2s and the O 2p bands. Also investigated is the case of a singly occupied defect level (an F+ center). This is done by reducing both the total number of electrons in the supercell and the background positive charge by one electron in the self-consistent electronic structure calculations. The optical transitions between the occupied and excited states of the: F and F+ centers are also investigated and found to be anisotropic in agreement with optical data.

Enhanced charge collection in polymer photovoltaic cells by using an ethanol-soluble conjugated polyfluorene as cathode buffer layer

We report enhanced polymer photovoltaic (PV) cells by utilizing ethanol-soluble conjugated poly (9, 9-bis (6'-diethoxylphosphorylhexyl) fluorene) (PF-EP) as a buffer layer between the active layer consisting of poly(3-hexylthiophene)/[6, 6]-phenyl C61-butyric acid methyl ester blend and the Al cathode. Compared to the control PV cell with Al cathode, the introduction of PF-EP effectively increases the shunt resistance and improves the photo-generated charge collection since the slightly thicker semi-conducting PF-EP layer may restrain the penetration of Al atoms into the active layer that may result in increased leakage current and quench photo-generated excitons. The power conversion efficiency is increased ca. 8% compared to the post-annealed cell with Al cathode.

生物－热催化过渡带沉积成岩演化及其成烃作用研究

The biothermocatalytic transitional zone gas is a new type of natural gas genetic theory, and also an clean, effective and high quality energy with shallow burial depth, wide distribution and few investment. Meanwhile, this puts biothermocatalytic transitional zone gas in important position to the energy resource and it is a challenging front study project. This paper introduces the concept, the present situation of study and developmental trend about biothermocatalytic transitional zone gas in detail. Then by using heat simulating of source rocks and catalysis mechanism analysis in the laboratory and studying structural evolution, sedimentation, diagenesis and the conditions of accumulation formation and so on, this paper also discusses catalytic mechanism and evolutionary model of the biothermocatalytic transitional zone gas formation, and establishes the methods of appraisal parameter and resources prediction about the biothermocatalytic transitional zone gas. At last, it shows that geochemical characteristics and differentiated mark of the biothermocatalytic transitional zone gas, and perfect natural gas genetic theory, and points out the conditions of accumulation formation, distribution characteristics and potential distribution region on the biothermocatalytic transitional zone gas m China. The paper mainly focuses on the formation mechanism and the resources potential about the biothermocatalytic transitional zone gas. Based on filed work, it is attached importance to a combination of macroscopic and microcosmic analysis, and the firsthand data are obtained to build up framework and model of the study by applying geologic theory. Based on sedimentary structure, it is expounded that structural actions have an effect on filling space and developmental cource of sediments and evolution of source rocks. Carried out sedimentary environment, sequence stratigraphy, sedimentary system and diagenesis and so on, it is concluded that diagenesis influences developmental evolution of source rocks, and basic geologic conditions of the biothermocatalytic transitional zone gas. Applying experiment simulating and catalytic simulating as well as chemical analysis, catalytic mechanism of clay minerals is discussed. Combined diagenecic dynamics with isotope fractionation dynamics, it is established that basis and method of resource appraisal about the biothermocatalytic transitional zone gas. All these results effectively assess and predict oil&gas resources about the biothermocatalytic transitional zone gas-bearing typical basin in China. I read more than 170 volumes on the biothermocatalytic transitional zone gas and complete the dissertation' summary with some 2.4 ten thousand words, draw up study contents in some detail and set up feasible experimental method and technologic course. 160 pieces of samples are obtained in oilfield such as Liaohe, Shengli, Dagang and Subei and so on, some 86 natural gas samples and more than 30 crude oil samples. Core profiles about 12 wells were observed and some 300 geologic photos were taken. Six papers were published in the center academic journal at home and abroad. Collected samples were analysised more than 1000 times, at last I complete this dissertation with more than 8 ten thousand words, and with 40 figures and 4 plates. According to these studies, it is concluded the following results and understandings. 1. The study indicates structural evolution and action of sedimentary basin influence and control the formation and accumulation the biothermocatalytic transitional zone gas. Then, the structural action can not only control accommodation space of sediments and the origin, migration and accumulation of hydrocarbon matters, but also can supply the origin of energy for hygrocarbon matters foramtion. 2. Sedimentary environments of the biothermocatalytic transitional zone gas are lake, river and swamp delta- alluvial fan sedimentary systems, having a warm, hot and humid climate. Fluctuation of lake level is from low to high., frequency, and piling rate of sedimentary center is high, which reflect a stable depression and rapidly filling sedimentary course, then resulting in source rocks with organic matter. 3. The paper perfects the natural gas genetic theory which is compound and continuous. It expounds the biothermocatalytic transitional zone gas is a special gas formation stage in continuous evolutionary sequence of organic matter, whose exogenic force is temperture and catalysis of clay minerals, at the same time, having decarbxylation, deamination and so on. 4. The methodology is established which is a combination of SEM, TEM and Engery spectrum analysis to identify microstructure of crystal morphology about clay minerals. Using differential thermal-chromatographic analysis, it can understand that hydrocarbon formation potential of different typies kerogens and catalytic method of all kinds of mineral matrix, and improve the surface acidity technology of clay minerals measured by the pyridine analytic method. 5. The experiments confirm catalysis of clay minerals to organic matter hygrocarbon formation. At low temperature (<300 ℃), there is mainly catalysis of montmorillonite, which can improve 2-3 times about produced gas of organic matters and the pyrolyzed temperature decreased 50 ℃; while at the high temperature, there is mainly catalysis of illite which can improve more than 2 times about produced gas of organic matters. 6. It is established the function relationship between organic matter (reactant) concentration and temperature, pressure, time, water and so on, that is C=f (D, t). Using Rali isotope fractionation effect to get methane isotope fractionation formula. According to the relationship between isotope fractionation of diagenesis and depth, and combined with sedimentary rate of the region, it is estimated that relict gas of the biothermocatalytic transitional zone gas in the representative basin. 7. It is revealed that hydrocarbon formation mechanism of the biothermocatalytic transitional zone gas is mainly from montmorillonite to mixed minerals during diagenesis. In interlayer, a lot of Al~(3+) substitute for Si~(4+), resulting in a imbalance between surface charge and interlayer charge of clay minerals and the occurrence of the Lewis and Bronsted acid sites, which promote to form the carbon cation. The cation can form alkene or small carbon cation. 8. It is addressed the comprehensive identification mark of the biothermo - catalytic transitional zone gas. In the temproal-spatial' distribution, its source rocks is mainly Palaeogene, secondly Cretaceous and Jurassic of Mesozoic, Triassic, having mudy rocks and coal-rich, their organic carbon being 0.2% and 0.4% respectively. The vitrinite reflection factor in source rocks Ro is 0.3-0.65%, a few up to 0.2%. The burial depth is 1000-3000m, being characterized by emerge of itself, reservoir of itself, shallow burial depth. In the transitional zone, from shallow to deep, contents of montmorillonites are progressively reduced while contents of illites increasing. Under SEM, it is observed that montmorillonites change into illite.s, firstly being mixed illite/ montmorillonite with burr-like, then itlite with silk-like. Carbon isotope of methane in the biothermocatatytic transitional zone gas , namely δ~(13)C_1-45‰- -60 ‰. 9. From the evolutionary sequence of time, distribution of the biothermocatalytic transitional zone gas is mainly oil&gas bearing basin in the Mesozoic-Neozoic Era. From the distribution region, it is mainly eastern stuctural active region and three large depressions in Bohaiwang basin. But most of them are located in evolutionary stage of the transitional zone, having the better relationship between produced, reservoir and seal layers, which is favorable about forming the biothermocatalytic transitional zone gas reservoir, and finding large gas (oil) field.

北京周边地区沙尘基的数值模拟与风成物质的REE分析

The sandstorms in 2001 were numerically simulated with NARCM that is a dust emission and transport model developed by Meteorological Service of Canada. In this paper, the dataset of NARCM model is processed and analyzed. The results of processing and analyzing show fair images about influence ranges and transport routes of sandstorms in 2001. The outcomes are compared with aerosol concentrations of atmosphere over Beijing, China and Tango, Japan. It confirms that sandstorm occurs when AK TK K and Si concentration in the air increases. It can be concluded that the NARCM model is appropriate for modeling sandstorm in North of China. The processing and analyzing show that the dust is produced and transported in the Otindag and Bashang. So the Otindag and Bashang are parts of source areas of sandstorms in East Asia. Another focus of this study is the REE of aeolian sediments in Otindag、Bashang、Tianmo Badain Jara、Hulunbeier and Kalahali, South Africa. The analysis on REE shows: There is clear distinction in HREE and LREE's Fractionation Degree (HLFD) between the deserts. HLFD is very high in Hulunbeier, with a value of (La/Lu)N 16.0. The value of (La/Lu)N is 12.7 inTianmo and 8.1 in Octindag. The HREE's Fractionation Degree(HFD) is about 4.0, quite similar in all samples. (3) The LREE's Fractionation Degree(LFD) varies slightly, from 1.5(Badain Jaran) to 2.3(Tianmo).

矾山杂岩体成因及其与磷（铁）矿的成矿关系

The Fanshan complex consists of layered potassic ultramafic-syenite intrusions. The Fanshan apatite (-magnetite) deposit occurs in the Fanshan complex, and is an important style of phosphorus deposit in China. The Fanshan complex consists of three (First- to Third-) Phases of intrusion, and then the dikes. The First-Phase Intrusive contains ten typical layered rocks: clinopyroxenite, biotite clinopyroxenite, coarse-grained biotite clinopyroxenite, pegmatitic orthoclase-biotite clinopyroxenite, variegated orthoclase clinopyroxenite, interstitial orthoclase clinopyroxenite, biotite rock, biotite-apatite rock, biotite rock and magnetite-apatite rock. This layered intrusive consists of nine rhythmic units. Each rhythmic unit essentially comprises a pair of layers: clinopyroxenite at the bottom and biotite clinopyroxenite at the top. The apatite (-magnetite) deposit is situated near the top of rhythmic Unit no. 6 of the First-Phase Intrusive. The Second-Phase Intrusive contains three typical rocks: coarse-grained orthoclase clinopyroxenite, . coarse-grained salite syenite and schorlomite-salite syenite. The Third-Phase Intrusive includes pseudo-trachytic salite syenite, porphyritic augite syenite, fine-grained orthoclase clinopyroxenite and fine-grained salite syenite. The origin of the Fanshan complex is always paid attention to it in China. Because most layered igneous intrusion in the world not only have important deposit in it, but also carry many useful information for studying the formation of the intrusion and the evolvement of magma. Two sketch maps were drawn through orebodies along no. 25 cross-cut on 425 mL and no. 1 cross-cut on 491 mL in the Fanshan mine. Through this mapping, a small-scaled rhythmic layering (called sub-rhythmic layering in the present study) was newly found at the top of the rhythmic Unit no. 6. The concept of sub-rhythmic layering is defined in this article. The sub-rhythmic layering is recognized throughout this apatite-rich part, except for magnetite-apatite rock. Presence of the layered magnetite-apatite rock is one of the characteristics of the Fanshan apatite (-magnetite) deposit. Thus, from this layer downwards six units of sub-rhythmic layering are recognized in the present study. Each unit consists of biotite clinopyroxenite (or biotite rock and biotite-apatite rock) layer at the bottom and apatite rock layer at the top. To study this feature in detail is an important work for understanding the origin of the Fanshan complex and apatite (-magnetite) deposit. The origin of the Fanshan complex and the relation of the formation of the apatite(-magnetite)deposit will be interpreted by the study of sub-rhythmic layering on the basis of previous research works. The magma formed the Fanshan complex was rich in K2O, early crystallized pyroxene, and after this phase more biotite crystallized, but no amphibole appeared. This indicated that the activity of H2O in the magma was low. Major element compositions of biotite and clinopyroxene (on thin sections) in the sub-rhythmic layering were analyzed using electron microprobe analyzer. The analytical results indicate Mg/(Mg+Fe*+Mn) atomic ratios (Fe*, total iron) of these two minerals rhythmically changed in sub-rhythmic layering. The trends of Mg/(Mg+Fe*+Mn) atomic ratio (Fe*, total iron) of biotite and clinopyroxene indicate that the magma evolved markedly from relatively magnesian bottom layer to less magnesian top layer in each sub-rhythmic unit. A general trend through the sub-rhythmic layering sequence is both minerals becoming relatively magnesian upwards. The formation temperatures for sub-rhythmic layering yield values between 600 and 800 ℃, were calculated using the ratio of Mg/(Mg+Fe+Mn) in the salite and biotite assemblage. The equilibrium pressures in the rhythmic layers calculated using the contents of Al in the salite were plotted in the section map, shown a concave curve. This indicates that the magma formed the First-Phase Intrusive crystallized by two vis-a-vis ways, from its bottom and top to its centre, and the magnetite-apatite rock was crytallized in the latest stage. The values of equilibrium pressures in the sub-rhythmic layering were 3.6-6.8(xlO8) Pa with calculated using the contents of Al in the salite. The characteristics of geochemistry in various intrusive rocks and the rocks or apatite of sub-rhythmic layers indicated that the Fanshan complex formed by the comagmatic crystallization. The contents of immiscible elements and REEs of apatite rock at the top of one sub-rhythmic unit are more than biotite clinopyroxenite at the bottom. The contents of immiscible elements and REEs of apatite of biotite clinopyroxenite at the bottom of one sub-rhythmic unit are higher than apatite rock at the top. The curves of rocks (or apatite) in the upper sub-rhythmic units are between two curves of the below sub-rhythmic unit in the primitive mantle-normalized trace element abundance spider diagram and the primitive mantle-normalized REE pattern. The trend for the contents of immiscible elements and REEs inclines to the same contents from the bottom to the top in sub-rhythmic layering. These characteristics of geochemistry of rocks or apatites from sub-rhythmic layering indicate that the latter sub-rhythmic unit was produced by the residual magma after crystallization of the previous sub-rhythmic unit. The characteristics of petrology, petrochemistry, geochemistry in the Fanshan complex and sub-rhythmic layers and the trends of Mg/(Mg+Fe+Mn) atomic ratio of biotite and clinopyroxene in sub-rhytmic layering rejected the hypotheses, such as magma immiscibility, ravitational settling and multiple and pulse supplement of magma. The hypothesis of differentiation by crystallization lacks of evidences of field and excludes by this study. On the base of the trends of formation temperatures and pressures, the characteristics of petrology, petrochemistry, geochemistry for the Fanshan complex and the characteristics of geochemistry for the rocks (or apatites), the trends of Mg/(Mg+Fe+Mn) atomic ratio of biotite and clinopyroxene in sub-rhytmic layering, and the data of oxygen, hydrogen, strontium and neodymium isotopes, this study suggests that the magma formed the Fanshan complex was formed by low degree partial melting of mantle at a low activity of H2O, and went through the differentiation at the depth of mantle, then multiply intruded and crystallized. The rhythmic layers of the First-Phase Intrusive formed by the magma fractional crystallized in two vis-a-vis ways, from the bottom and top to the centre in-situ fractional crystallization. The apatite (-magnetite) deposit of the Fanshan complex occurs in sub-rhythmic layering sequence. The the origin of the sub-rhythmic layering is substantially the origin of the Fanshan apatite (-magnetite) deposit. The magma formed the rhythmic layers of First-Phase Intrusive was rich in H2O, F and P at the later stage of its in-situ fractional crystallization. The Fanshan apatite (-magnetite) deposit was formed by this residual magma in-situ fractional crystallization. The magnetite-apatite rock was crystallized by two vis-a-vis ways at the latest stage in-situ fractional crystallization in the rhythmic layers. The result was light apatite layer below heavy the magnetite-apatite layer, formed an "inversion" phenomenon.

A high-resolution solid-state NMR study on nano-structured HZSM-5 zeolite

Variations in the structure and acidity properties of HZSM-5 zeolites with reduction in crystal sizes down to nanoscale (less than 100 nm) have been investigated by XRD, TEM and solid-state NMR with a system capable of in situ sample pretreatment. As evidenced by a combination of Al-27 MAS NMR, Si-29 MAS, CP/MAS NMR and H-1 MAS NMR techniques, the downsize of the zeolite crystal leads to an obvious line broadening of the Al-27, Si-29 MAS NMR spectrum, an increasing of the silanol concentration on the external surface, and a pronounced alteration of the acidity distribution between the external and internal surfaces of the zeolite. In a HZSM-5 zeolite with an average size at about 70 nm, the nonacidic hydroxyl groups (silanols) are about 14% with respect to the total amount of Si, while only 4% of such hydroxyl groups exist in the same kind of zeolite at 1000 nm crystal size. The result of H-1 MAS NMR obtained using Fluorinert(R) FC-43 (perfluorotributyl amine) as a probe molecule demonstrates that most of the silanols are located on the external surface of the zeolite. Moreover, the concentration of Bronsted acid sites on the external surface of the nano-structured zeolite appears to be distinctly higher than that of the microsized zeolite.

A novel method to synthesize amorphous silica-alumina materials with mesoporous distribution without using templates and pore-regulating agents

In this study, a novel sol-gel method is used to synthesize amorphous silica-alumina materials with a narrow mesoporous distribution and various Si/Al molar ratios without using any templates and pore-regulating agents. During the preparation procedure, only inexpensive inorganic salts were used as raw materials, instead of expensive and harmful alkoxides. The precursor sol was dried at room temperature in a vacuum box kept at 60 mmHg until it began to form the gel. The results of a nitrogen sorption experiment indicate that the synthesized materials with different Si/Al molar ratios have similar mesoporous distributions (within 2-12 nm). Moreover, it was found that the material's pore size distribution remains at a similar value during the heat treatment from room temperature to 550 degreesC. On the basis of the nitrogen sorption, TEM, and AFM characterization results, a formation mechanism of mesopores which accounts for the experimental data is also suggested. This suggested mechanism involves rearrangement of the primary particles during the drying process to form the precursors of the similarly sized mesopores. The synthesized materials were characterized by XRD, thermal analysis (TG/DTA), Al-27 and Si-29 MAS NMR spectroscopy, SEM, TEM, and AFM. The results of Al-27 and 29Si MAS NMR indicate that the distribution of silicon and aluminum in the synthesized materials is more uniform and homogeneous than that in the mixed oxides prepared via the traditional sol-gel method even at high alumina contents. The type and density of the acid sites were studied using pyridine adsorption-desorption FTIR spectroscopy. It was shown that the acidity of the synthesized materials is higher than that of the silica-alumina materials prepared by conventional methods.

Sol-gel derived oxides and mixed oxides catalysts with narrow mesoporous distribution

A novel sol-gel process for preparing oxides and mixed oxides sols from precipitation and peptization process is reported in this article. Inorganic salts are used as raw materials in this study. It is found that the amount of acid has great influence on the stability and particle diameter distribution of the precursor sols. Ultrasonic treatment is used to prepare alumina sol at room temperature. The result of Al-27 NMR shows that there exist Al-13(7+) species in the sol. By controlling the sol particles with narrow particle diameter distribution, alumina, titania and silica-alumina (SA) materials with narrow mesoporous distribution are formed by regular packing of sol particles during gelation without using any templates. The results also show that the structure and particle diameter distribution of precursor sol determine the final materials' texture.

New route for light olefins production from chloromethane over HSAPO-34 molecular sieve

HSAPO-34 molecular sieve was employed in chloromethane conversion and showed high performance in activity and selectivity in production of light olefins. Our detailed IR investigation allowed the identification of the active sites and the adsorbed species and demonstrated that the conversion started from 350 degrees C with alkoxy group as the intermediate. The fixed-bed catalytic testing evidenced that in the range of 350-500 degrees C, 70-80% of chloromethane was transferred to ethylene, propylene and butenes. Increasing reaction temperature favors the conversion and enhances the yield of lighter olefins. A very important reversible phenomenon, the breaking of Al-O-P bonds upon adsorption of HCl, a main product of reaction to generate a large amount of P-OH groups and the recovery of Al-O-P upon removal of HCI was revealed. (c) 2005 Elsevier B.V. All rights reserved.