MgCO3分子的解离产物合成MgAl2O4分子

本研究碳酸镁MgCO₃分子的解离过程及其解离产物与三氧化二铝Al₂O₃合成MgAl₂O₄的微观过程．利用Gaussian 09软件采用CCSD(T) 6-311++G(d,p)和M06-2x/6-311++G(d,p)方法分别计算反应物碳酸镁MgCO₃分子单点能和频率,并计算反应物受热分解的过程,寻找解离的过渡态.并通过高温烧结法,在实验室用MgCO₃和Al₂O₃粉末为原料,1450℃合成铝酸镁MgAl₂O₄,通过X-ray diffraction即XRD测试表征实验产物与理论计算是一致的.     

Sonochemical preparation of high surface area MgAl2O4 spinel

High surface area MgAl(2)O(4) has been synthesised by a sonochemical method. Two kinds of precursors were used, alkoxides and nitrates/acetates and in both cases nanostructured MgAl(2)O(4) was obtained. The effect of the addition of a surfactant during the sonication, cetyl trimethyl ammonium bromide, was also investigated. In the case of alkoxides precursors the as-made product is a mixture of hydroxides of aluminium and magnesium, while with nitrates/acetates a gel is obtained after sonication, containing the metal hydroxides and ammonium nitrate. Heating at 500 degrees C transforms the as-made products into MgAl(2)O(4) spinel phase. The surface area is up to 267m(2)/g after treatment at 500 degrees C and 138m(2)/g at 800 degrees C.     

La0.7Ca0.3MnO3/MgAl2O4复合样品的电输运特性

我们用传统的固相反应法制备了(La0.7Ca0.3MnO3)1-x(MgAl2O4)x复合样品.通过XRD分析发现在此系列复合样品中La0.7Ca0.3MnO3和MgAl2O4两相共存;电阻率温度关系分析表明MgAl2O4的引入没有改变母体相在温度TP1处本征的金属-绝缘体转变峰,但使复合样品在较低温度TP2处出现另外一个电阻率峰值.有趣的是,随着MgAl2O4掺量的增加,在低掺量时,TP2向低温偏移很快;但在高掺量时,TP2向低温偏移较慢.     

水热-溶胶-凝胶法制备高比表面积MgAl2O4尖晶石

以金属硝酸盐为原料,聚乙烯醇为稳定剂,在200℃水热反应温度下制备了氧化铝和氧化镁凝胶经700℃焙烧4h后获得高纯度、结晶完整的镁铝尖晶石(MgAl2O4).用XRD、TG-DTA、SEM和BET等表征结果表明,加入PVA-124可以对胶体粒子起到保护作用,阻止胶粒因热运动碰撞而聚集,并使铝、镁氧化物胶粒均匀混合,在较...     

溶胶-凝胶法制备SiO2基片Er3+∶Al2O3光学薄膜

用溶胶凝胶法在SiO2 基片上提拉制备了掺Er3 + ∶Al2 O3 光学薄膜。采用扫描电子显微镜、原子力显微镜、差热热重分析仪、X射线衍射仪研究了掺Er3 + ∶Al2 O3 光学薄膜的形貌和结构特性。在 90 0℃烧结后 ,SiO2 基片上提拉 15次形成厚度 8μm掺摩尔比 0 .0 1Er3 + 的面心立方结构γ Al2 O3 薄膜具有明显 (110 )择优取向 ,掺摩尔比 0 .0 1Er3 + 对γ Al2 O3 的晶体结构和结晶生长过程未产生显著影响。薄膜具有均匀多孔结构 ,平均粒径为 30～ 10 0nm ,平均孔径为 5 0～ 10 0nm ,表面起伏度为 10～ 2 0nm。掺摩尔比 0 .0 1Er3 + ∶γ Al2 O3 薄膜 ,获得了中心波长为1.5 34μm(半峰全宽为 36nm)的光致发光谱。     

Adsorption of CO_2 on MgAl layered double hydroxides: Effect of intercalated anion and alkaline etching time

The adsorption of CO_2 on MgAl layered double hydroxides(MgAl-LDHs) based adsorbents has been an effective way to capture CO_2,however the adsorption capacity was hampered due to the pore structure and the dispersibility of adsorption active sites.To address the problem,we investigate the effect of intercalated anion and alkaline etching time on the structure,morphology and CO_2 uptake performances of MgAl-LDHs.MgAl-LDHs are synthesized by the onepot hydrothermal method,followed by alkaline etching of NaOH,and characterized by x-ray diffraction,N_2 adsorption,scanning electron microscopy and Fourier transform infrared spectroscopy.The CO_2 adsorption tests of the samples are performed on a thermogravimetric analyzer,and the adsorption data are fitted by the first-order,pseudo-second-order and Elovich models,respectively.The results demonstrate that among the three intercalated samples,MgAl(Cl) using chloride salts as precursors possesses the highest adsorption capacity of CO_2,owing to high crystallinity and porous structure,while MgAl(Ac) employing acetate salts as precursors displays the lowest CO_2 uptake because of poor crystallinity,disorderly stacked structure and unsatisfactory pore structure.With regard to alkaline etching,the surface of the treated MgAl(Cl) is partly corroded,thus the specific surface area and pore volume increase,which is conducive to the exposure of adsorption active sites.Correspondingly,the adsorption performance of the alkaline-etched adsorbents is significantly improved,and MgAl(Cl)-6 has the highest CO_2 uptake.With the alkaline etching time further increasing,the CO_2 adsorption capacity of MgAl(Cl)-9 sharply decreases,mainly due to the collapse of pore structure and the fragmentized sheet-structure.Hence,the CO_2 adsorption performance is greatly influenced by alkaline etching time,and appropriate alkaline etching time can facilitate the contact between CO_2 molecules and the adsorbent.     

Atomistic and electronic structure calculation of defects at the surfaces of oxides

We present the results of simulations using both atomistic and density functional theory (DFT) approaches that illustrate the uses of these techniques for investigating the structure and electronic structure of defects at the surfaces of oxides. Atomistic simulation studies of the low index surfaces of spinel (MgAl 2 O 4 ) will show the role of vacancy configuration and surface rearrangement. Atomistic and DFT studies on Li doped MgO illustrate the importance of both the defect structure and its effect of morphology. We will also illustrate using DFT electronic defects at the surface of CeO 2 , which are of great importance in redox reactions and catalytic activity. Finally we will present a novel atomistic approach for predicting the structure of supported oxide nanoclusters giving rise to a wide range of defects including a range of surface terminations, grain formation, mixed screw edge dislocations and misfit dislocations. We will illustrate this using the structure of a BaO supported MgO nanocluster.     

Cr3+∶MgAl2O4晶体的基态能级分裂及Jahn-Teller效应*

构造了3d3/3d7离子在三角对称晶场中考虑自旋-轨道相互作用,自旋-自旋相互作用和自旋-其它轨道相互作用的120阶微扰哈密顿矩阵.利用完全对角化该矩阵的方法计算了Cr3+∶MgAl2O4晶体的基态能级、零场分裂参量,理论计算值与实验值相符合.定量研究了自旋二重态对基态能级的贡献,证明该贡献是不可忽略的.定量研究了自旋-轨道相互作用、自旋-自旋相互作用和自旋-其它轨道相互作用对Cr3+∶MgAl2O4晶体的光谱精细结构和零场分裂参量的影响,发现自旋-轨道和自旋-自旋相互作用对基态能级和零场分裂参量的影响的程度和方式是不同的,自旋-其它轨道相互作用的影响也是不可忽略的.通过理论计算值和实验值的比较,证实了在Cr3+∶MgAl2O4晶体中Jahn-Teller效应的存在,解释了该晶体的光谱精细结构的成因.     

V-doped MgAl6O10:novel luminescence substrate for phosphor-free UV-white LEDs

V-doped MgAl6O10 is grown by the conventional Czochralski method. The crystal structure and the cell parameters are analyzed through X-ray diffraction experiments. The absorption and emission spectra are investigated. Under pumping at 324 nm, the emission spectra of V-doped MgAl6O10 obtain two emission peaks at the wavelengths of 471 and 570 nm. Two emission bands of the spectra combine to produce a spectrum that is perceived as white by the naked eye. Therefore, V-doped MgAl6O10 single crystal can be applied as substrate for phosphor-free ultraviolet (UV)-white light-emitting diodes (LEDs).     

Eu2+掺杂浓度对BAM光谱特性的影响

采用燃烧法在低温成功合成了纳米Ba1-xMgAl10O17:xEu2 (0.05≤x≤0.4)蓝色荧光粉,着重研究了Eu2 掺人量对荧光粉光谱特性的影响.利用XRD和SEM对材料的物相和形貌进行了分析,采用荧光光谱仪测定了样品的发光特性.结果表明,合成的产物为纯相,且颗粒细小、分布均匀,平均粒径约30 nm.Eu2 的掺杂浓度对样品的发光性能有显著的影响,随Eu2 浓度增大,发光中心增多,Eu2 离子间相互作用增强,能量传递加快,发光强度逐渐增大.当Eu2 浓度为x=0.2时,能量传递速率与发射速率相等,Euz 的发光达到最大值;此后,随Eu2 的浓度进一步增加,Eu2 之间的能量传递速率将超过发射速率,Eu2 还未将光发射出去就发生能量的传递,使激发能通过晶格的迁移而消耗,呈现浓度猝灭特性.     

Stability of a flexible polar ionic crystal surface: metastable alumina and one-dimensional surface metallicity

A first-principles study of kappa-Al2O3 (001) and (001-) reveals new features of ion-surface stability and electronic structure. The need to generalize Tasker's rules for surface stability of low-symmetry crystals is shown. Structurally, the presence of bulk tetrahedral Al ( Al(T)) causes giant surface relaxations, with O termination at (001). Surface-layer Al(T) are strongly unfavored. This is understood with Pauling's rules and thus generally applicable to metastable aluminas. The bulk charge asymmetry and Al-sublattice anisotropy caused by the Al(T) create a 1D metallic surface state at (001-).     

Mechanism of oxygen adsorption on surfaces of γ-TiAl

We studied the adsorption behavior of oxygen on low index surfaces of γ-TiAl via first principles to investigate the mechanism that drives the adsorption behavior. The (100) surface is the most stable surface energetically followed by the (111), (110) and (001) surfaces. A study of the adsorption of a single oxygen atom on surfaces of TiAl showed that the O atom prefers the Ti-rich environment that has a high potential of generating TiO₂. Competition between O-Al bonding and O-Ti bonding was observed in the O adsorbed surface regions. However, the O-Ti interaction dominates the adsorption behavior in all considered systems except when O is adsorbed on an Al-terminated (001) surface as the O–Al bond is stronger than O–Ti bond. A linear relationship between adsorption energy and integration of orbital overlaps between the O atom and the metals is obtained, which indicates that the electronic structure controls the adsorption behavior of an O atom on a γ-TiAl surface — an opportunity to improve the oxidation resistance of γ-TiAl based alloys.     

CuO/Al2O3、CuO/CeO2-Al2O3和CuO/La2O3-Al2O3催化剂中CuO物种被CO氧化的比较

用浸渍法制备了CuO/Al2O3 (Cu/Al)、CuO/CeO2- Al2O3 (Cu/CeAl)和CuO/La2O3-Al2O3(Cu/LaAl)催化剂. 通过原位XRD、Raman和H2-TPR方法， 对催化剂中的CuO物种以及CuO-Al2O3的固-固相反应进行了表征. 结果表明，对于Cu/Al催化剂，CuAl2O4存在于CuO与Al2O3层之间，CuO以高分散和晶相两种相态存在于催化剂的表层；对于Cu/CeAl催化剂，除了少量高分散和晶相的CuO存在于表层外，大部分CuO迁移到了CeO2的内层，     

绿色长余辉材料MgAl_2O_4∶Mn~(2+)的合成及其发光特性

采用高温固相法在1350℃下合成了Mn2+掺杂的MgAl2O4发光材料,利用X射线衍射对所合成样品的结构进行了表征。用209nm的紫外灯照射样品后,观察到来自Mn2+的4T1-6A1跃迁的绿色长余辉发光。发光的激发光谱表明:Mn2+-3d组态内存在一系列强的激发峰,分别在279,361,386,427,451nm,同时还有209nm处的Mn-O电荷迁移带,激发该吸收带会产生很强的绿色余辉。测量了余辉的衰减曲线及热释光谱,分析了Mn2+掺杂浓度对样品余辉性质的影响,给出了余辉产生的可能模型。     

利用电子束蒸发制备铝隧道结工艺研究

采用电子束蒸发的方法在Si片上制备超导铝(Al)薄膜。利用X射线衍射和直流四电极电阻法分别测试了厚度从100埃到5000埃的Al薄膜物向组成,超导转变温度(Tc)和临界电流密度(Jc)。当Al薄膜厚度大于500埃时,超导转变温度Tc=1.2K。电子束蒸发制备的Al薄膜性能良好,具有较高的结晶质量,为制备Al超导隧道结奠定了良好基础。对小面积的Al超导隧道结工艺进行了研究,该超导隧道结两层的超导体材料为Al薄膜,中间势垒层材料为Al2O3。其中Al薄膜利用电子束蒸发制备,势垒层通过直接氧化Al薄膜表面实现,该工艺和采用直接蒸发氧化物薄膜工艺相比不仅简单而且能有效防止势垒层不连续造成的弱连接。     

Ba2+掺杂对Sr3Al2O6:Eu2+红色荧光粉发光性能的影响

采用高温固相法合成了(Sr1-x-yBax)3Al2O6∶3yEu2+红色荧光材料,通过XRD、荧光光谱和热稳定性测试分析,分别研究了Eu2+、Ba2+掺杂对样品的晶体结构、发光性能和热稳定性的影响。XRD测试结果表明,在1 200℃保温3 h条件下合成了具有立方晶体结构、空间群为Pa3的Sr3Al2O6纯相样品,Eu2+、Ba2+的掺入并没有改变其基质晶格的结构类型。荧光光谱分析表明,Eu2+的摩尔分数为4%时,(Sr0.98-yBa0.02)3Al2O6∶3yEu2+样品的发射峰最强,Ba2+的掺入使样品的发射峰发生红移而发射强度降低,且随Ba2+浓度的增加红移越发明显。此外,Ba2+的掺杂提高了Sr3Al2O6∶Eu2+样品的热稳定性。     

Synthesis of Magnetic Metal Organic Framework Fe3O4 @ NH2-MIL-53 (Al) Materials and Application to the Adsorption of LeadSCIEI北大核心CSCD

Metal organic framework, a novel class of organic inorganic hybrid functional materials, has been widely used in the fields of gas adsorption, catalysis, separation, and biological medicine due to its large specific surface area, diverse structural, and adjustable channel. In this work, a new amine-functionalized magnetic metal-organic framework material was synthesized. Nano-Fe3O4 was prepared by a solvothermal method, after which polyvinyl pyrrolidone was employed to modify Fe3O4. Finally, amino groups were introduced to prepare Fe3O4@NH2-MIL-53(Al). The crystal structure and functional groups of the material were characterized by means of X-ray diffraction (XRD) and Fourier transform infrared spectrometry (FT-IR). Combined with flame atomic absorption spectroscopy (FAAS), the adsorption of lead by the magnetic adsorbent was investigated. The magnetic adsorbent possesses high adsorption capacity because of the large specific surface area of Fe3O4@NH2-MIL-53 (Al) and the coordination between amino group and lead. Experimental conditions affecting the adsorption percentage were discussed and the experimental operation parameters were optimized (pH value of 6.0 and adsorption time of 120 min). Kinetics and thermodynamics studies were conducted for the adsorption process. Langmuir/Freundlich and pseudo-first-order/pseudo-second-order models were applied to analyze the experimental data. Thermodynamic functions, i.e., changes of Gibbs energy, entropy, and enthalpy, were calculated from temperature experiments. In addition, the regeneration of the adsorbent was considered with hydrochloric acid as the desorption solution. Several adsorption and desorption experiments were carried out, illustrating that the Fe3O4@NH2-MIL-53(Al) adsorbent can be used repeatedly.     

Reactive wetting: H2O/Rh(111)

First-principles calculations imply that neither H2O bilayers nor half-dissociated, H2O+OH+H monolayers are thermodynamically stable on clean Rh(111). Thus, the experimental observation that Rh(111) supports a periodic 2D water adlayer needs an explanation. Chemistry involving common surface impurities, notably C atoms, may be the answer. Calculations show they provide favorable binding sites for H atoms detached from H2O. The resulting OH fragments can anchor a 2D water layer to the surface.     

Investigation of a 4H-SiC metal-insulation-semiconductor structure with an Al2O3/SiO2 stacked dielectric

Atomic layer deposited(ALD) Al2O3 /dry-oxidized ultrathin SiO2 films as a high-k gate dielectric grown on 8°off-axis 4H-SiC(0001) epitaxial wafers are investigated in this paper.The metal-insulation-semiconductor(MIS) capacitors,respectively with different gate dielectric stacks(Al2O3/SiO2,Al2O3,and SiO2) are fabricated and compared with each other.The I-V measurements show that the Al2O3/SiO2 stack has a high breakdown field(≥12 MV/cm) comparable to SiO2,and a relatively low gate leakage current of1×10-7A/cm2 at an electric field of4 MV/cm comparable to Al2O3.The 1-MHz high frequency C-V measurements exhibit that the Al2O3/SiO2 stack has a smaller positive flat-band voltage shift and hysteresis voltage,indicating a less effective charge and slow-trap density near the interface.     

氧化铝与Al(100)基体间界面原子结构研究

本文介绍了用MeV离子散射和沟道效应研究单晶铝表面无定型氧化层与基体之间界面原子结构的方法。报道了Al₂O₃/Al(100)界面原子结构的实验结果。实验表明,在纯氧气氛围中400℃下生成的氧化铝膜,铝和氧原子浓度比例严格为2与3之比;Al₂O₃膜和Al(100)基体之间的界面极其陡峭,氧化铝膜下Al(100)基体表面的再构层不大于一个原子层。由实验测量与用Monte Carlo方法计算结果比较,得到再构层原子离开原来晶 关键词：