溶胶-凝胶法制备MoP/SiO2催化剂加氢脱硫催化活性的研究

以正硅酸乙酯为硅源,以钼酸铵和磷酸二氢铵为钼源和磷源,采用溶胶-凝胶法,经干燥、焙烧,程序升温还原制备得到二氧化硅负载磷化钼(MoP)催化剂。以噻吩、二苯并噻吩为模型化合物,对负载催化剂的加氢脱硫活性进行评价,考察了负载量、反应压力、反应温度等因素对催化活性的影响。实验结果表明,MoP/SiO₂催化剂Mo的最佳负载量为20%,升高反应压力和温度均有利于提高二苯并噻吩的转化率,但降低了产物中联苯的含量。     

Multipeak-structured photoluminescence mechanisms of as-prepared and oxidized Si nanoporous pillar arrays

Silicon dominates the electronic industry, but its poor optical properties mean that it is not preferred for photonic applications. Visible photoluminescence (PL) was observed from porous Si at room temperature in 1990, but the origin of these light emissions is still not fully understood. This paper reports that an Si nanocrystal, silicon nanoporous pillar array (Si-NPA) with strong visible PL has been prepared on a Si wafer substrate by the hydrothermal etching method. After annealing in O₂ atmosphere, the hydride coverage of the Si pillar internal surface is replaced by an oxide layer, which comprises of a great quantity of Si nanocrystal (nc-Si) particles and each of them are encapsulated by an Si oxide layer. Meanwhile a transition from efficient triple-peak PL bands from blue to red before annealing to strong double-peak blue PL bands after annealing is observed. Comparison of the structural, absorption and luminescence characteristics of the as-prepared and oxidized samples provides evidence for two competitive transition processes, the band-to-band recombination of the quantum confinement effect of nc-Si and the radiative recombination of excitons from the luminescent centres located at the surface of nc-Si units or in the Si oxide layers that cover the nc-Si units because of the different oxidation degrees. The sizes of nc-Si and the quality of the Si oxide surface are two major factors affecting two competitive processes. The smaller the size of nc-Si is and the stronger the oxidation degree of Si oxide layer is, the more beneficial for the luminescent centre recombination process to surpass the quantum confinement process is. The clarification on the origin of the photons may be important for the Si nanoporous pillar array to control both the PL band positions and the relative intensities according to future device requirements and further fabrication of optoelectronic nanodevices.     

快速冷冻干燥法制备多孔氧化硅陶瓷

为制备氧化硅多孔陶瓷,尝试了快速冷冻干燥法,探索了氧化硅浆体的分散剂和pH值对孔结构的影响.结果表明:使用0.1wt;六偏磷酸钠作为分散剂时,孔壁处团聚现象明显;改用聚甲基丙烯酸钠团聚显著减少.主要原因是氧化硅表面的Si-OH可能与六偏磷酸钠络合成Si-Na4P6O18-,但其在水中易断裂,减弱了颗粒之间排斥力,未能抑制团聚;而聚甲基丙烯酸钠吸附在氧化硅表面,可能形成Si-C4H5O2等空间位阻抑制团聚.在聚甲基丙烯酸钠的基础上再调节浆体pH值至～10使氧化硅的zeta电位达到～-60 mV,可更好抑制团聚.综上所述冻干法适合制备开口通孔结构的多孔氧化硅陶瓷.     

热处理对富硅氧化硅薄膜中硅纳米晶形成的影响

采用磁控溅射法制备了富硅氧化硅薄膜, 然后分别经过一步热处理、两步热处理和快速热处理制备了镶嵌有硅纳米晶的氧化硅薄膜. 实验结果表明, 在硅含量为～ 42.63 at.%的富硅氧化硅薄膜中, 三种热处理均能形成10¹²/cm²量级的硅纳米晶. 其中在两步热处理中, 硅纳米晶的密度最高, 达到2.2× 10¹²/cm², 并且尺寸均匀、结晶完整性好; 一步热处理后的样品中, 硅纳米晶密度较低, 并且部分纳米晶结晶不充分; 快速热处理后的样品中, 硅纳米晶密度最低、尺寸分布不均匀, 并且存在孪晶结构. 分析认为, 热处理初始阶段的形核过程对纳米晶的密度及微观结构有着重要的影响, 两步热处理中的低温段促进了纳米晶的成核, 有助于形成高密度高质量硅纳米晶.     

脉冲偏压占空比对多孔氧化硅薄膜性质的影响

采用由脉冲负偏压调节的等离子体增强化学气相沉积方法,以硅烷为源气体,在玻璃基片上沉积得到了多孔二氧化硅薄膜。将反应过程中加在沉积区域的脉冲偏压固定在-350V,当占空比从0.162增大到0.864时,薄膜样品的形貌、成份和结构均不相同。扫描电镜照片表明,组成多孔氧化硅薄膜的颗粒在占空比增大时变得细腻,并且薄膜整体变得多孔且蓬松。拉曼光谱和红外光谱结果显示,薄膜样品中的非晶硅和Si-H键在较高的占空比下减弱甚至消失。占空比升高时氧化硅桥键所占比例持续增加。     

The Role of Silicon Oxide Layers in Luminescence of Ensembles of Silicon Quantum Dots

Based on the quantum confinement-luminesecence center model,to ensembles of spherical silicon nanocrystals (nc-Si)containg two kinds of luminescence centers(LCs) in the SiOx layers surrounding the nc-Si,the relationship between the photolumincescence(PL) and the thickness of the SiOx layer is studied with the excitation energy flux density as a parameter.When there is no SiOx layer surrounding the nc-Si,the electron-heavy hole pair can only recombine inside the nc-Si,then the PL bluehift with reducing particle sizes roughly accords with the rule predicted by the quantum confinement model of Canham.When there presences a SiOx layer,some of the carriers may tunnel into it and recombine outside the nc-Si at the LCs to emit visible light.The thicker the SiOx layer is,the higher the radiative recombination rate occurred outside the nc-Si will be.When the central Scale of the nc-Si is much smaller than the critical scale,the radiative recombination rate outside the nc-Si dominates,and visible PL will be possible for some nc-Si samples with big average radius,greater than 4nm,for example.When there is only one kind of LC in the SIOx layer,the PL peak position does not shift with reducing particle sizes.All these conclusions are in accord with the experimental results.When there are two or more kinds of LCs in the SiOx layer,the PL peak position energy and intensity swing with reducing particle sizes.     

线型脲醛树脂的半结晶模板化作用

酸性条件下硅溶胶体系中尿素和甲醛聚合反应会产生脲醛树脂-氧化硅杂化沉淀. 沉淀的质量随有机组分比例的增加而增加, 当尿素和甲醛物质的量比≥1.0时生成沉淀的量为恒定最大值. 红外分析表明杂化材料在3348, 1635, 1572和784 cm^－1处产生了可被归结为线型结构(—[NHCONHCH₂]_n—)的特征吸收. XRD分析表明这种线型分子可形成氢键(C＝O…H—N)导向型的半结晶. 微分热重和XRD结果证明结晶物种在290 ℃完全分解. SEM表征显示半结晶杂化沉淀以三维网络结构为特征, 具有层状结晶的各向异性, 其初级粒子即使在室温下干燥也容易开裂. 随着反应时间的延长、酸性的增加或无机组分量的相对增加杂化粒子变得更加致密. 液氮吸附结果证明沉淀焙烧后所得氧化硅材料的结构具有层状孔结构性质, 其比表面积、孔尺寸和孔体积可以达到510 m²/g, 14.3 nm和1.68 cm³/g. 改变反应体系的酸性和反应组分配比等条件可以方便地控制杂化材料的结构.     

高岭土凝胶及氧化硅的制备与光谱性质研究

高岭土经氢氧化钠活化后与盐酸反应制备了硅铝酸盐凝胶,所得硅铝酸盐凝胶经过干燥与酸化处理得到氧化硅。利用红外光谱(IR)、X射线衍射(XRD)和X荧光光谱(XRF)对所得硅铝酸盐凝胶及氧化硅进行了表征研究,探索了高岭土制备硅铝酸盐凝胶的最佳条件。结果表明,高岭土矿为40 g时制备硅铝酸盐凝胶和氧化硅的最佳条件为：氢氧化钠用量15～20 g、盐酸浓度4～5 mol·L-1;IR,XRD及XRF表征结果显示,最终产物具有氧化硅的结构且其纯度较好。     

小角x射线散射方法研究甲基改性氧化硅干凝胶的孔结构

以正硅酸乙酯［Si(OC2H5)4，TEOS］为前驱体制备SiO2悬浮液，分别以甲基三乙氧基硅烷［CH3Si(OC2H5)3，MTES］和二甲基二乙氧基硅烷［(CH3)2Si(OC2H5)2，DDS］为前驱体制备硅氧烷聚合物溶液，通过混合法得到两种不同的甲基改性氧化硅凝胶-测量了凝胶的散射强度，计算了凝胶的孔径分布、平均孔径DSAXS、界面层厚度E等参数，结合氮气吸附实验，分析了凝胶的孔结构-发现SiO2一次簇团被MTES聚合物或DDS聚合物连接为二次簇团时产生微孔，同时甲基随聚合物连接于凝胶骨架上形成与 关键词： 小角x射线散射 甲基改性氧化硅 干凝胶 孔结构     

Covalently Attached Monolayer of Phthalocyanine on Chemically Modified Silicon Oxide Surface

Highly stable monolayers of 2,9,16,23-tetracarboxyl phthalocyanine on 3-aminopropyl-triethoxysilane (ATS) modified silicon and quartz substrates were prepared by reaction of carboxyl and amine. The monolayers were characterized by UV-Vis spectra and AFM measurements. The results indicated that the ultra-thin films on silicon or quartz were smooth, and the ordered structures were observed in these films.