模板法合成含镧的层状无机-有机纳米复合材料

以表面活性剂十二烷基磺酸钠为模板制备了含稀土元素La的无机-有机纳米复合材料。通过XRD、SEM、HRTEM、EDX等的表征，证明所得的稀土复合物为层状结构，且十二烷基磺酸钠与La的比例为1∶1。考察了反应温度、反应时间以及原料配比等对复合物结构的影响。     

Calcined Ni—Al layered double hydroxide as a catalyst for total oxidation of volatile organic compounds: Effect of precursor crystallinity

The effect of hydrothermal treatment on properties (crystallinity, porous structure, reducibility, acidity, basicity, and catalytic activity and selectivity in toluene and ethanol total oxidation) of Ni—Al layered double hydroxide precursors and related mixed oxides was examined. The hydrothermal treatment increased considerably both the content of crystalline phase and LDH crystallite size. On the other hand, only a slight effect of the precursor hydrothermal treatment on crystallinity of the related Ni—Al mixed oxides obtained by calcination at 450°C was observed. The reducibility of NiO particles appeared to be hindered considerably compared to the reducibility of pure NiO. Catalytic activity of the Ni—Al mixed oxides prepared from the precursors hydrothermally treated for a short time (4 h) was the highest. The highest amount of acetaldehyde formed during the total oxidation of ethanol, i.e. the worst selectivity was found for the calcined Ni—Al LDH without hydrothermal treatment. Presented at the 33rd International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 22–26 May 2006.     

用于超级电容器的层状Co3O4/Ti纳米片柔性电极及其低电荷转移电阻

采用水热合成法,在Ti网上原位生长多孔层状Co_3O_4纳米片,并优化了电荷转移电阻。通过X射线衍射(XRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)对产物的结构、形貌进行表征,及对电极的电化学性能进行测试。结果表明,材料是由排列良好的微米矩形二维薄片组成,且具有均匀的孔隙分布。这种独特的微纳米结构的超级电容器电极材料降低了电极的电荷转移电阻,增强了活性物质的结构稳定性,从而提高了电极的电化学性能,在电流密度为100 mA·g-1时,电极循环1 000次后,电容保持率为91.8%,电荷转移电阻(Rct)为0.29Ω。这些显著的超电容性能归因于合理的二维层状结构在柔性基底钛网上的生长及柔性Co_3O_4/Ti电极活性材料的高利用率。     

An Ultra‐Long‐Life Lithium‐Rich Li1.2Mn0.6Ni0.2O2 Cathode by Three‐in‐One Surface Modification for Lithium‐Ion Batteries

Voltage decay and capacity fading are the main challenges for the commercialization of Li‐rich Mn‐based layered oxides (LLOs). Now, a three‐in‐one surface treatment is designed via the pyrolysis of urea to improve the voltage and capacity stability of Li_1.2Mn_0.6Ni_0.2O₂ (LMNO), by which oxygen vacancies, spinel phase integration, and N‐doped carbon nanolayers are synchronously built on the surface of LMNO microspheres. Oxygen vacancies and spinel phase integration suppress irreversible O₂ release and help lithium ion diffusion, while N‐doped carbon nanolayer mitigates the corrosion of electrolyte with excellent conductivity. The electrochemical performance of LMNO after the treatment improves significantly; the capacity retention rate after 500 cycles at 1 C is still as high as 89.9 % with a very small voltage fading rate of 1.09 mV cycle^?1. This three‐in‐one surface treatment strategy can suppress the voltage decay and capacity fading of LLOs.     

以酚醛树脂为碳源原位合成富锂层状相/尖晶石/碳核壳结构正极材料及其电化学性能

通过酚醛树酯包覆和碳热反应在富锂正极材料表面原位构建碳和尖晶石双壳保护结构, 对这种核壳结构的正极材料进行了结构和形貌表征, 并研究了其电化学性能. 研究发现, 尖晶石相为材料提供了三维锂离子迁移通道, 碳包覆层显著提高了正极材料的电子电导率, 两种效应的共同作用极大降低了材料的电化学阻抗, 提升了材料的放电比容量, 这种多壳层结构正极材料还具有优异的倍率性能, 在5C倍率下放电比容量可达到135.1 mA·h/g.     

Self‐Pillared,Single‐Unit‐Cell Sn‐MFI Zeolite Nanosheets and Their Use for Glucose and Lactose Isomerization

Single‐unit‐cell Sn‐MFI, with the detectable Sn uniformly distributed and exclusively located at framework sites, is reported for the first time. The direct, single‐step, synthesis is based on repetitive branching caused by rotational intergrowths of single‐unit‐cell lamellae. The self‐pillared, meso‐ and microporous zeolite is an active and selective catalyst for sugar isomerization. High yields for the conversion of glucose into fructose and lactose to lactulose are demonstrated.     

改性层状双氢氧化物对铜离子(Ⅱ)和双酚A的协同吸附

采用离子交换法制备了十二烷基苯磺酸根(DBS^-)和柠檬酸根(Cit^3-)复合改性层状双氢氧化物(LDHs),简写为DBS-Cit-LDHs。 利用粉末X射线衍射分析、红外光谱分析、比表面积测定以及元素分析等技术手段对样品进行了表征。 结果表明,DBS^-和Cit^3-已柱撑进入LDHs层间。 研究了DBS-Cit-LDHs对水中重金属离子Cu²⁺和有机污染物双酚A(BPA)的协同吸附性能。 吸附实验结果表明,DBS-Cit-LDHs能同时高效去除Cu²⁺和BPA;对Cu²⁺的强吸附能力缘于DBS-Cit-LDHs层间Cit^3-与Cu²⁺形成了稳定配合物;对BPA的强吸附能力缘于分配作用,且吸附能力与样品比表面积无关。 DBS-Cit-LDHs对Cu²⁺的吸附动力学和热力学分别符合准二级动力学方程和Freundlich等温式;对BPA的吸附分别符合准一级动力学方程和Linear等温式。 二者吸附过程的ΔG^o和ΔH^o均为负值,表明吸附为自发放热过程。     

层状、花形和棒状钛酸铋纳米结构的可控合成及光催化性能

通过可控水热法,制备出层状、花形和棒状钛酸铋(Bi4Ti3O12,BIT)纳米结构。通过X射线衍射(XRD)和场发射扫描电子显微镜(FESEM)观测其结构和形貌特征。XRD图显示,所制备的样品为层状钙钛矿结构。FESEM结果表明,通过控制水热过程的反应参数可以得到不同形貌的纳米粉体。紫外-可见漫反射光谱(UV-Vis DRS)表明BIT样品的带隙能约为2.63～2.95 eV。利用可见光(λ>420 nm)照射下的甲基橙降解实验评价了BIT样品的光催化性能。结果表明,BIT的光催化活性比掺氮TiO2(N-TiO2)高得多。所制备的层状BIT纳米结构光催化效率最高,经可见光照射360 min,甲基橙溶液的降解率可达95.0%。同时还研究了结构和形貌对不同条件下制备的BIT样品光催化活性的影响。     

CP@NiAl-LDH复合材料的制备及其超级电容器性能

通过采用简易温和的水热条件制备导电聚合物@镍铝层状双金属氧化物复合材料（CP@NiAl-LDH）,构建电子/离子的高速传输纳米通道,利用SEM和XRD对复合材料结构形貌进行表征。电化学性能测试结果表明,导电聚合物为复合材料提供一定的赝电容,促进电荷的快速转移,使CP@NiAl-LDH的电容性能得以显著提升。PPy@LDH具有最好的电容性能,在1 A·g^-1的电流密度下,其比容量高达3 010.3 F·g^-1,当电流密度升高到20 A·g^-1时,其比电容保持率为73.1%,表现出优异的倍率性能;同时,在10 A·g^-1的电流密度下10 000次充放电循环后仍具有88.8%的比容量保持率,具有优异的循环稳定性。这主要归功于NiAl-LDH与导电聚合物之间的协同增强效应。     

Phase Separation in Methylsiloxane Sol-Gel Systems in a Small Confined Space

The organo-siloxane gel with co-continuous structure derived from methyltrimethoxysilane (MTMS) was synthesized in a confined space between parallel plates by inducing spinodal decomposition during sol-gel transition. The resultant gel morphology was 3-dimensionally observed by laser scanning confocal microscopy (LSCM). The sliced LSCM photographs revealed that the confined gels have inhomogeneity perpendicular to the plate, exhibiting a layered structure. The layered structure can be divided into three regions according to their morphology; interface, near-surface layer, bulk phase. The organo-siloxane depletion layer had formed in the vicinity of both hydrophobic and hydrophilic plates, and the bulk phase had formed slight away from the plates exhibited co-continuous structure. In addition, the confined gels exhibited no shrinkage during drying process that resulted in the larger domain size compared to the monolithic gel. The attractive interaction between the plates and the resultant organo-siloxane phase accounts for the inhibition of shrinkage of confined gels.