Influence of Fe2O3 and V2O5 on Crystalline Structure of Mg-Al Spinel Synthesized by Waste Aluminum Slag

Mg-Al spinel is synthesized by using industrial waste-residue and basic magnesium carbonate in the aluminum factory as the main raw materials. The influence of V2O5 and Fe2O3 mineralizers on the structure, cell parameters and microscopic morphology of synthesized Mg-Al spinel has been discussed. The Mg-Al spinel is characterized by using XRD, SEM and relevant analytical software, such as Philips plus, Rietveld quantification and so on. The experimental results show that certain amounts of V2O5 and Fe2O3 are beneficial to the formation of Mg-Al spinel, and the optimum addition of V2O5 and Fe2O3 is respectively 2wt% and 3wt%. V2O5 has few effects on cell parameters of Mg-Al spinel; but Fe2O3 can form solid solution with Mg-Al spinel in which Mg-Fe spinel can also dissolve to form continuous solid solution. Therefore, with the increase of Fe2O3 content, the cell parameters of Mg-Al approximately present linear increase.     

Mg-Al-O-t-Bu hydrotalcite as an efficient catalyst for the transesterification of dimethyl carbonate with ethanol

Mg-Al-O-t-Bu hydrotalcite was synthesized and characterized by XRD, FT-IR and TGA-DTA. It was proved to be an active heterogeneous catalyst for the transesterification of dimethyl carbonate (DMC) with ethanol. When the reaction was carried out over Mg-Al-O-t-Bu hydrotalcite at 80°C, 7 h, molar ratio of ethanol to DMC 5:1, 1.0 wt.% of catalyst, the conversion of DMC was 86.4%, the selectivity to diethyl carbonate (DEC) was 61.2%. This heterogeneous catalyst could be used 5 times without loss of its activity.     

镁铝混合氧化物负载镍催化剂的制备及在液化石油气低温重整反应中的催化性能

采用共沉淀-浸渍法制备了不同Ni 含量的 Ni/Mg(Al)O 催化剂并用于液化石油气(LPG)的低温水蒸气重整反应. X 射线衍射和程序升温还原结果表明, 在 800 ℃焙烧的 Ni/Mg(Al)O 催化剂中, NiO 与 MgO 反应生成 Mg-Ni-O 固溶体, 还原后形成金属 Ni 纳米颗粒. 详细研究了 Ni 含量(质量分数)、反应温度和水/碳摩尔比(n_H2O/n_C) 等对催化剂性能的影响. 实验结果表明, 15%Ni/Mg(Al)O 催化剂对 LPG 低温重整反应具有最佳的催化性能. 提高反应温度能显著提高 Ni/Mg(Al)O 催化剂的催化性能. 当n_H2O/n_C=2时, 在400~500 ℃的温度范围使LPG完全转化的最大反应空速从 28900 mL·h^-1·g^-1Cat提高到 86800 mL·h^-1·g^-1Cat. 适当增大水/碳摩尔比有利于 LPG 转化为小分子气体, 但在 LPG 摩尔流量不变的情况下, 反应气中水含量过高会导致 LPG 转化率降低. 反应后催化剂的X射线衍射谱(XRD)和热重分析(TG)结果表明, Ni/Mg(Al)O催化剂优良的催化活性和反应稳定性可归因于催化剂表面Ni晶粒较高的稳定性和抗积炭性能.     

镁铝水滑石层板与层间阴离子相互作用的理论研究

本文采用以ASED-MO(含原子对排斥的EHMO法)为基础的结构自动优化的EHTOPT程序,对镁铝水滑石(LDHs)层板与层间阴离子相互作用进行了理论研究.以Mg6Al2(OH)16X@H2O为分子结构单元,计算并分析了与不同层间阴离子形成稳定结构的能量变化、成键状况及电荷转移情况,揭示了层间作用力的本质.结果表明,LDHs层板与层间阴离子间存在静电吸引、氢键等非共价键弱相互作用,且氢键作用为主,其强弱与阴离子电荷分布、空间排布方式密切相关;层间阴离子电荷分布同时还影响着层板酸碱性的变化.     

氧化铝基表层镁铝尖晶石的研究──Ⅰ．表层镁铝尖晶石的相结构、孔结构、表面酸性及负载钯的化学状态

对＜１０００℃焙烧的γ－Ａｌ２Ｏ３载镁体系进行了相表征，发现在基质氧化铝上形成了表层镁铝尖晶石，具有“原尖晶石结构”的γ－Ａｌ２Ｏ３则在＜１０００℃保持物相不变．进一步研究了这种氧化铝基表层镁铝尖晶石的孔结构、表面酸性以及负载耙的分散与化学状态，结果表明：氧化铝基表层尖晶石的孔结构和表面酸性由构成的氧化铝基决定，并随温度变化，表层尖晶石仅可稳定氧化铝基的物相，与其孔性质和酸性无关；负载在氧化铝基表层尖晶石上的钯，主要分布在表层镁铝尖晶石上，有强的载体一金属相互作用，以Ｐｄ０和Ｐｄ２＋两种状态存在．     

Mechanism of pore formation and structural characterization for mesoporous Mg-Al composite oxides

Mg-AI layered double hydroxides (LDH) with different particle sizes were prepared using different aging times at high supersaturation by a new method developed in our laboratory. The key features of this method are a very rapid mixing and nucleation process followed by a separate aging process. By calcination of LDH at 500癈, mesoporous Mg-AI composite oxides with an extremely narrow pore size distribution were produced. The crystal structure of the Mg-AI composite oxides was a multiphasic one consisting of MgO-like crystals and a layered material.     

Exploring the potential energy surfaces of association of NO with aminoacids and related organic functional groups: the role of entropy of association

Association between NO and each of the 20 amino acids and their related organic functional groups was studied by exploring the configuration space of the potential energy of association surface by using the multiple minima hypersurface procedure. AM1 semiempirical Hamiltonian was used in order to explore such complex hypersurfaces of biological molecular interactions at finite computational times. An appropriate test with a set of NO and small molecule complexes obtained at the MP2/6-311++g(2d,2p) level of theory was also carried out. Stabilization energies of larger models were also evaluated at the conventional PBE1PBE/6-31g(d,p) DFT level. NO–aminoacid hypersurface explorations yielded that interactions of NO with NH group together with the C=O belonging to the backbone appeared predominant in all cases. Models of polar aminoacids and NO also show stable interactions with the lateral chains. Interactions with charged amino acids were found as the most stable and Lys was, undoubtedly, the preferred association. The study of these kinds of interactions must take into account the deepest and other minima because the entropy of association plays an important role. Contribution to the Serafin Fraja Memorial Issue. Dedicated to Prof. Serafín Fraga, an unforgettable friend.     

基于MgAl-8-HQ LDH复合粒子选择性检测Fe~(3+)的荧光传感器

为实现对Fe~(3+)高选择和简便检测,基于镁铝层状双氢氧化物(MgAl LDH)层板的Al~(3+)的可调控性及易与8-羟基喹啉(8-HQ)发生配位作用,设计制备了8-HQ插层配位的高荧光性8-羟基喹啉镁铝层状双氢氧化物(Mg_xAl-8-HQ LDH),同时采用IR,XRD,UV-Vis及分子荧光光谱仪表征其结构和性能。IR分析表明8-HQ与铝离子生成C-O-Al和C-N-Al配位键;XRD揭示8-HQ插入MgAl LDH的层板间,致(003)衍射峰向2θ低角度方向移动,衍射峰强度随Mg与Al摩尔比增加而增强;因MgAl LDH层间的8-HQ与Al~(3+)配位,致8-HQ在314 nm处的吸收峰消失,同时在376 nm处出现了金属离子与配体之间的跃迁吸收峰;荧光分析表明:Mg_xAl-8-HQ LDH的荧光强度随Al~(3+)含量降低而增强,当镁铝离子物质的量之比为4∶1时,荧光强度显著强于8-羟基喹啉铝。通过研究金属离子对Mg_4Al-8-HQ LDH粒子荧光光谱的影响,发现该粒子对金属离子表现出显著的选择和差异性,尤其对Fe~(3+)具有高选择性。进一步研究[Fe~(3+)]对Mg_4Al-8-HQ LDH粒子的溶液颜色及荧光强度的影响表明:在10~(-6)~10~(-2)mol·L~(-1)内随[Fe~(3+)]增加,Mg_4Al-8-HQ LDH粒子溶液的颜色由浅黄色变成墨绿色,故可实现上述浓度范围内Fe~(3+)的比色传感;同时其荧光强度显著降低,当[Fe~(3+)]为10~(-3)mol·L~(-1)可完全猝灭其荧光,当-log[Fe~(3+)]为3~6时,-log[Fe~(3+)]与溶液荧光强度呈负相关函数关系,可实现对Fe~(3+)的高选择和灵敏性荧光传感检测,据此本实验成功建立了Mg_A Al-8-HQ LDH粒子荧光和比色双重传感检测Fe~(3+)的新方法。     

稀土对镁-铝合金抗热裂性能的影响及其机制

研究了稀土（0.1%～1.2%,质量分数）对Mg-Al合金抗热裂性能的影响及其机制.结果表明： 往Mg-Al合金中添加稀土后,合金的抗热裂性能显著下降,其原因可归为： 稀土引起了Mg-Al合金晶粒粗化,使得热裂纹萌生所需的断裂应变降低;稀土减少了Mg-Al合金中的共晶组织,缩短了枝晶通道保持开通的时间,不利于合金进行补缩;而且稀土还提高了共晶反应的温度,使得凝固后期枝晶间液膜的强度有所下降;当α-Mg枝晶连成骨架时,分布在枝晶间的Al11RE3相容易堵塞枝晶通道,增加了合金补缩的难度;Al11RE3相与α-Mg基体的凝固收缩率不同,容易产生凝固收缩应力,促进热裂纹的萌生.     

Studies on the Influence of Sintering Temperature on Crystalline Structures of Mg-Al Spinel Synthesized by Waste Aluminum Slag

Mg-Al spinel is synthesized by using industrial waste-residue and basic mag- nesium carbonate in the aluminum factory as the main raw materials. The influence of sintering temperature on crystalline structure and microstructure of Mg-Al spinel has been mainly discussed. The crystalline structure of sample is characterized by using XRD, SEM and relevant analytical software. The experimental results show that compared to the conventional synthetic method, the application of waste aluminum slag as the raw material can greatly decrease the synthetic tem- perature. The content of Mg-Al spinel first increases and then decreases with the rise of sintering temperature, and its purity can reach as high as 96wt% at 1550 ℃, which is therefore determined to be the optimum synthetic temperature. SEM observations demonstrate that as the rise of sintering temperature, the grain of Mg-Al spinel grows up obviously with typical octahedral characteristic appearance.