近紫外激发Gd2ZnTiO6∶Eu3+,Li+红色荧光粉的制备及荧光性能

采用溶胶-凝胶法成功制备出系列Eu³⁺掺杂和Li⁺、Eu³⁺共掺杂Gd₂ZnTiO₆红色荧光粉,并研究Li⁺、Eu³⁺掺杂对样品的晶体结构、微观形貌及发光性能的影响。结果显示,所制备的Gd₂ZnTiO₆∶Eu³⁺,Li⁺(GZT∶Eu³⁺,Li⁺) 荧光粉为双钙钛矿结构,属于单斜晶系(空间群:P2₁/n),大小为10 μm的无规则形状的颗粒。在395 nm近紫外光的激发下,GZT∶Eu³⁺的发射光谱展示出典型的Eu³⁺线状特征光谱,发射峰中心位于615 nm处,归属于Eu³⁺的⁵D₀→⁷F₂跃迁。Eu³⁺的最佳掺杂浓度为0.07(摩尔分数),样品显示明显的浓度猝灭效应,其机制为电偶极子-电偶极子(d-d)相互作用。此外,研究还发现,Li⁺掺杂对样品的晶体结构、微观形貌没有影响,但是一定量的Li⁺掺杂可以显著增强样品的荧光强度。当Li⁺浓度为0.05时,荧光粉发射主峰强度增强程度最大,提高至原来的4.3倍,说明通过Li⁺、Eu³⁺共掺杂可以获得高亮度的GZT红色荧光粉。GZT∶0.14Eu³⁺,0.05Li⁺荧光粉的CIE色坐标为(0.631 1,0.375 3)与标准红光色坐标(0.670,0.330)较为接近,是一种潜在的LED用红色荧光粉。     

Deciphering Internal and External π-Conjugation in C3-Symmetric Multiple Azobenzene Connected Systems in Self-Assembly

Two tripodal C₃-symmetric photoswitchable molecular systems T1 and T2 are reported that have extended conjugation at external and internal positions using an acryl group. The influence of the extended π-bonds in their absorption properties, thermal relaxation of the photoisomers and their propensities in forming supramolecular self-assemblies have been explored through spectroscopy, and microscopic studies. In particular, the investigations on the self-assembly have been carried out using scanning electron microscopy (SEM), transmission electron microscopy (TEM), polarized optical microscopy (POM), X-ray diffraction studies (XRD) and atomic force microscopy (AFM). Remarkably, the position of the acryl group influences the behaviour of the two target molecules in supramolecular assembly, and also in the formation of photoresponsive organic hydrogels or microcrystals.     

Heterogeneous Electrocatalytic Oxygen Evolution Reaction by a Sol-Gel Electrode with Entrapped Na3[Ru2(μ-CO3)4]: The Effect of NaHCO3

The Na₃[Ru₂(μ-CO₃)₄] complex is acting as a water oxidation catalyst in a homogeneous system. Due to the significance of heterogeneous systems and the effect of bicarbonate on the kinetic, we studied the bicarbonate effect on the heterogeneous electrocatalyst by entrapping the Na₃[Ru₂(μ-CO₃)₄] complex in a sol-gel matrix. We have developed two types of sol-gel electrodes, which differ by the precursor, and are demonstrating their stability over a minimum of 200 electrochemical cycles. The pH increases affected the currents and k_cat for both types of electrodes, and their hydrophobicity, which was obtained from the precursor type, influenced the electrocatalytic process rate. The results indicate that NaHCO₃ has an important role in the catalytic activity of the presented heterogeneous systems; without NaHCO₃, the diffusing species is probably OH⁻, which undergoes diffusion via the Grotthuss mechanism. To the best of our knowledge, this is the first study to present a simple and fast one-step entrapment process for the Na₃[Ru₂(μ-CO₃)₄] complex by the sol-gel method under standard laboratory conditions. The results contribute to optimizing the WSP, ultimately helping expand the usage of hydrogen as a green and more readily available energy source.     

溶胶-凝胶法制备NixCo1-xCoAlO4尖晶石型复合氧化物及其催化分解N2O性能

用溶胶凝胶法制备了一组Ni_xCo_1-xCoAlO₄尖晶石型复合氧化物,并采用表面润湿浸渍K₂CO₃溶液进行了K掺杂改性,用于有氧气氛下的N₂O催化分解反应.采用N₂物理吸附、X-射线衍射(XRD)、扫描电镜(SEM)、H₂-程序升温还原(H₂-TPR)等技术对催化剂进行了表征,考察了催化剂组成、母液pH值、K负载量等制备参数对其催化活性的影响.结果表明,母液pH值为3、K/(Ni+Co)物质的量比为0.1的K/Ni_0.15Co_0.85CoAlO₄催化剂具有较高的N₂O分解活性,450 ℃ N₂O可完全分解.助剂K的加入弱化了催化剂表面金属氧键,提高了催化剂的还原性、催化活性和抗水性.     

含氟CaO-P2O5-SiO2-Na2O-B2O3玻璃陶瓷的制备及性能表征

采用溶胶-凝胶法制备CaO-P₂O₅-SiO₂-Na₂O-B₂O₃体系前驱体粉末,用CaF₂替代部分CaO再次制备前驱体粉末。 通过TG-DSC分析确定结晶温度为865 ℃,经过热处理获得主晶相为Na₆Ca₃Si₆O₁₈的玻璃陶瓷。 通过X射线衍射(XRD)、傅里叶红外光谱(FTIR)、扫描电子显微镜(SEM)等技术手段及体外生物活性实验分析玻璃陶瓷的显微结构及性能。 结果表明,CaF₂的加入能提高玻璃陶瓷的体积密度、抗折强度和弹性模量,并且不会破坏玻璃陶瓷的生物活性。     

PW11Cu/TiO2膜光催化剂的制备及可见光催化性能

以PW₁₁Cu为可见光活性组分,TiO₂为载体结构组分,采用溶胶-凝胶法制备了PW₁₁Cu/TiO₂复合膜可见光催化剂,并用UV-Vis DRS、IR、Raman、XRD、SEM、TEM等手段对催化剂的光吸收性质、化学组成、晶相、表面结构和形貌进行了表征,同时,以模型污染物RhB的可见光降解为探针评估了它的光催化活性,考察了膜处理温度、PW₁₁Cu含量和溶液酸性对催化活性的影响,最后,通过催化剂循环降解RhB试验评估了PW₁₁Cu/TiO₂膜的稳定性。实验结果表明,PW₁₁Cu/TiO₂膜对可见光有明显吸收,低温(100℃)处理的膜为无定形态,高温(500℃)处理的膜为多晶态;低温处理的膜具有较高的可见光催化活性,用于RhB的可见光催化降解,在中性条件下反应80 min,RhB的降解率为100%,TOC去除达32%(4 h);提高溶液酸性有利于催化剂活性的提高,在pH=2.5的条件下,达到100%的RhB降解仅需30 min。在本实验条件下,PW₁₁Cu的最佳剂量是3.0 g。经过10次循环降解RhB,催化剂的光催化活性仍保留约90%。     

葡萄糖对溶胶凝胶法制备Li1.2Ni0.13Co0.13Mn0.54O2正极材料性能的影响

利用XRD、SEM、EDS、BET、激光粒度、循环伏安、恒流充放电、交流阻抗方法研究了葡萄糖为碳源对溶胶凝胶法制备Li_1.2Ni_0.13Co_0.13Mn_0.54O₂正极材料的结构、形貌以及电化学性能的影响。结果表明:与前驱体中未加入葡萄糖所制备的材料相比,掺葡萄糖后样品颗粒分布相对均匀,粒径变小,D₅₀从11.56减小至9.94μm,比表面积增加近1倍。经0.05C充放电活化后,未掺葡萄糖和掺葡萄糖样品0.2C放电比容量分别为183.4、211.6mAh·g^-1,2C容量分别为其0.2C的62.2%、77.6%。1C循环50次后放电比容量分别为133.3、173.6mAh·g^-1,容量保持率分别为95.1%、100%。掺葡萄糖可降低首次不可逆容量损失,提高材料的倍率性能与循环稳定性,减少电荷传递阻抗、Warburg阻抗以及双电层弥散效应,但不改变材料的晶型结构。     

EFFECTS OF FINELY DISPERSED METALLIC PALLADIUM ON MICROSTRUCTURE AND PROPERTIES OF NANOCOMPOSITES PRODUCED BY SOL-GEL TECHNIQUE

Nanosized palladium particles were incorporated into mesoporous silica matrix to obtain nanocomposites using the sol-gel technique. Effects of the finely dispersed metallic palladium on the microstructure and properties of the nanocomposites were investigated. By means of X-ray diffraction and optical absorption, it was found that palladium particles were 5-9 nm in diameter and their uniform dispersion in the mesoporous silica depended on both the content of the palladium and the structural features of the silica matrix. The results showed that the mixing method of preparation led to wider size distribution of the nanosized particles as compared to the immersion method, but dispersed degree was reduced. Although the incorporation of nanosized palladium particles could not substantially induce significant structural changes of the matrix, the apparent red-shifted optical absorptions for the nanocomposites were observed as compared to the parent monolithic silica, particularly with increase in palladium loading and calcination temperature.     

CARBON NANOTUBES VIA METHANE DECOMPOSITION ON AN ALUMINA SUPPORTED COBALT AEROGEL CATALYST

An alumina-supported cobalt aerogel catalyst prepared from a sol-gel and a supercritical drying method was used in the catalytic decomposition of methane.The physical-chemical properties of the catalyst were characterized and its activity for methane decomposition was investigated.The effects of calcination and reaction temperatures on the activity of the catalyst and the morphology of the carbon nanotubes produced were discussed.A COAl2O4 spinel structure formed in the calcined catalyst.The quantity of the nanotubes produced in the reaction increases with the amount of cobalt in the reduced catalyst.A higher reaction temperature leads to a higher reaction rate,though faster deactivation of the catalyst occurs with the change.The carbon nanotubes grown on the catalyst have smooth walls and uniform diameter distribution.     

N,Fe, La三掺杂锐钛矿型TiO2能带调节的理论与实验研究

采用基于密度泛函理论(DFT)的平面波超软赝势方法(PWPP), 利用Material studio 计算N, Fe, La三种元素掺杂引起的锐钛矿TiO₂晶体结构、能带结构和态密度变化. 并通过溶胶-凝胶法制得锐钛矿型本征TiO₂, N, Fe共掺杂TiO₂和N, Fe, La共掺杂TiO₂; 用X射线衍射和扫描电镜表征结构; 紫外-可见分光光度计检测TiO₂对甲基橙的降解效率变化. 计算结果表明, 由于N, Fe, La三掺杂TiO₂的晶格体积、键长等发生变化, 导致晶体对称性下降, 光生电子-空穴对有效分离, 同时在导带底和价带顶形成杂质能级, TiO₂禁带宽度由1.78 eV变为1.35 eV, 减小25%, 光吸收带边红移, 态密度数增加, 电子跃迁概率提升, 光催化能力增加. 实验结果表明: 离子掺杂使颗粒变小, 粒径大小: 本征TiO₂>N/Fe_TiO₂>N/Fe/La_TiO₂, 并测得N/Fe/La_TiO₂发光峰425 nm, 能隙减小, 光催化能力比N/Fe_TiO₂强, 增强原因是杂质能级和电子态数量增加引起.