固体核磁共振研究固体酸催化剂酸性进展

酸性直接与固体酸催化剂的活性相关,因此研究固体酸催化剂的酸性受到了科研工作者的广泛关注. 固体核磁共振技术已经成为研究固体酸催化剂酸性的一种强有力的工具. 该文介绍了固体核磁共振的特点和各种常用技术,着重综述了固体核磁共振研究固体酸催化剂酸性的进展.     

固体核磁共振技术在甲醇制烯烃反应中的应用

甲醇制烯烃过程是由非石油路线生成低碳烯烃的重要途径之一.分子筛因具备独特的孔结构和可调变的酸性质,而成为甲醇制烯烃过程的核心催化剂.固体核磁共振(NMR)是鉴定物质结构、阐释催化反应机理的强有力的工具,在甲醇制烯烃的研究中被广泛应用.本文主要总结了近年来利用原位固体NMR、多维多核NMR、脉冲梯度场NMR等固体NMR技术研究甲醇制烯烃反应机理取得的重要进展.原位固体NMR可以在真实反应条件下监测催化反应中反应物、中间体和产物的动态演变过程;多维多核NMR可以在不破坏催化剂结构情况下确定反应中间体结构信息,特别是¹²⁹Xe NMR可以很灵敏探测反应中催化剂的孔道结构变化;脉冲梯度场NMR可用于测定孔道内分子的扩散系数,阐明分子筛的扩散机制.     

H-SSZ-13分子筛催化乙醇脱水制乙烯反应的原位固体核磁共振研究

本文采用原位连续流动条件和间歇条件下的固体核磁共振技术,以及二维¹³C-¹³C基于偶极耦合的结合R2（COmbined R2 Driven,CORD）自旋扩散序列的核磁共振实验捕获了H-SSZ-13分子筛催化乙醇脱水过程中多种中间物种,并揭示了各种中间物种的动态演变过程.结果发现H-SSZ-13分子筛催化乙醇脱水过程中,存在两种不同吸附构型的乙醇、活化态的乙醚、乙氧基以及三乙基氧鎓离子,并首次通过原位固体核磁共振技术观测到乙烯的生成.这些结果加深了相关研究者对乙醇脱水反应的认识.     

多金属氧酸盐TBA3[VW5O19]及TBA4[PVW11O40]的固体核磁共振研究

多金属氧酸盐（简称多酸,Polyoxometalates,POMs)是由处于d⁰电子构型的前过渡金属元素通过共边或共角缩聚而成的金属-氧簇类化合物．由于其具有丰富的分子结构和独特的物理化学性质,已经被广泛应用于功能材料、催化化学和药物化学等领域．其中钒取代的多酸阴离子具有很好的催化活性,特别是对烃类的氧化,它的活性主要受钒取代的数目和钒中心的阴离子环境这两个因素影响．该文利用固体核磁技术分析了一取代钒的两类典型结构中⁵¹V的局域结构和化学环境,以及有机阳离子对多酸阴离子结构的影响,特别是对⁵¹V的化学环境的影响,为研究多酸的催化活性和催化机理提供基本的结构信息．     

Pt/TiO2催化剂的载体结构对甲醇催化氧化性能的影响

二氧化钛载体包括二氧化钛纳米管阵列(TNTAs)和二氧化钛纳米线阵列(TNWAs)两种,载体的结构不同对催化性能有一定的影响。然而,Pt负载在TNTAs和TNWAs催化性能的比较鲜有报道。本文通过微波法制备了Pt/TNTAs和Pt/TNWAs两种催化剂,结果表明,Pt/TNTAs催化甲醇氧化效果要优于Pt/TNWAs。相较于Pt/TNWAs, Pt/TNTAs的优越催化性能可能与纳米管的限域效应有关。可见,载体的结构对催化剂的性能有很大的影响。     

沸石^17O固体核磁共振研究进展

沸石作为一类最重要的固体氧化物材料,是17O固体核磁共振最早研究对象之一.近年来,随着核磁共振谱仪磁体场强的不断提高,以及新脉冲序列的发展,17O固体核磁共振被越来越多地应用于沸石的结构表征,在研究骨架氧结构以及测定Brnsted酸位的O-H键长等方面都提供了非常丰富的信息.本文将介绍17O固体核磁共振的特点,回顾20年来它在沸石研究方面的发展并着重介绍近期这一方面的研究突破.     

沸石17O固体核磁共振研究进展

沸石作为一类最重要的固体氧化物材料,是¹⁷O固体核磁共振最早研究对象之一. 近年来,随着核磁共振谱仪磁体场强的不断提高,以及新脉冲序列的发展,¹⁷O固体核磁共振被越来越多地应用于沸石的结构表征,在研究骨架氧结构以及测定Brønsted酸位的O-H键长等方面都提供了非常丰富的信息. 本文将介绍¹⁷O固体核磁共振的特点,回顾20年来它在沸石研究方面的发展并着重介绍近期这一方面的研究突破.      

催化精馏专用填料型固体酸SO42-/ZrO2-Al2O3-Al的研究

为了研制催化精馏专用催化剂 ,采用铝阳极氧化法制备了Al2 O3 Al一体型载体 ,并将活性固体超强酸SO42 -/ZrO2 引入到Al2 O3 Al上 ,得到一种新型催化精馏专用填料式固体酸SO42 -/ZrO2 Al2 O3 Al催化剂 .利用XRD、SEM、BET、XPS、NH3 TPD等手段对其进行了表征 .结果表明 ,所制得的阳极氧化铝膜厚为 5 6 μm ,SO42 -/ZrO2 Al2 O3 Al固体酸具有比表面积大、酸强度适中的特点 .XRD结果表明 ,ZrO2 在Al2 O3 Al上处于高度分散状态 .将该固体酸用于乙酸 /乙醇酯化反应中 ,显示出较高的催化活性 ,且稳定性较好     

光催化甲醇重整机理的原位核磁共振研究

本文利用原位核磁共振技术在真实固液反应环境中对光催化甲醇重整过程进行了研究.研究发现，体系中甲醇重整的液态中间产物主要有四种：HOCH₂OH、CH₃OCH₂OH、HCOOH和HCOOCH₃.不同晶型的二氧化钛催化剂会影响这四种产物的生成趋势.随光照时间的增加，上述四种产物的含量均会增加.Pd负载对一级中间产物CH₃OCH₂OH和HOCH₂OH的产率影响较大，其产率为无Pd负载的2~3个数量级；对二级中间产物HCOOCH₃和HCOOH的产率影响较小.     

Robust Low Voltage Program-Erasable Cobalt-Nanocrystal Memory Capacitors with Multistacked Al2O3/HfO2/Al2O3 Tunnel Barrier

A n atomic-layer-deposited Al2O3/HfO2/Al2O3 （A/H/A） tunnel barrier is in vestigated for Co nanocrystal memory capacitors. Compared to a single Al2O3 tunnel barrier, the A/H/A barrier can significantly increase the hysteresis window, i.e., an increase by 9 V for ±12 V sweep range. This is attributed to a marked decrease in the energy barriers of charge injections for the A/H/A tunnel barrier. Further, the Co-nanocrystal memory capacitor with the A/H/A tunnel barrier exhibits a memory window as large as 4.1 V for 100 μs program/erase at a low voltage of ±7 V, which is due to fast charge injection rates, i.e., about 2.4× 10^16 cm^-2 s^-1 for electrons and 1.9× 1016 cm^-2 s^-1 for holes.     

Excellent Passivation of p-Type Si Surface by Sol-Gel Al2O3 Films

Al2O3 films with a thickness of about lOOnm synthesized by spin coating and thermally treated are applied for field-induced surface passivation of p-type crystalline silicon. The level of surface passivation is determined by techniques based on photoconductance. An effective surface recombination velocity below lOOcm/s is obtained on 10Ωcm p-type c-Si wafers （Cz Si）. A high density of negative fixed charges in the order of 10^12 cm^-2 is detected in the Al2O3 films and its impact on the level of surface passivation is demonstrated experimentally. Furthermore, a comparison between the surface passivation achieved for thermal SiO2 and plasma enhanced chemical vapor deposition SiNx ：H films on the same c-Si is presented. The high negative fixed charge density explains the excellent passivation of p-type c-S/by Al2O3.     

Microwave Response of MgB2/A12O3 Superconducting Thin Films by Microstrip Resonator Technique

Double-sided superconducting MgB2 thin films are deposited onto c-A120a substrates by the hybrid physical chemical vapour deposition method. The microwave response of MgB2/A12O3 is investigated by microstrip resonator technique. A grain-size model is introduced to the theory of microstrip resonators to analyse microwave properties of the films. We obtain effective penetration depth of the films at OK （λe0 = 463nm） and surface resistance （R8 = 1.52 mΩ at 11 K and 8. 73 GHz） by analysing the resonant frequency and unload quality factor of the microstrip resonator, which suggests that the impurities and disorders of grain boundaries of MgB2/A12 Oa result in increasing penetration depth and surface resistance of the films.     

Memory Effect of Metal--Insulator--Silicon Capacitors with SiO2/HfO2/Al2O3 Dielectrics

Charge trapping characteristics of the metal-insulator-silicon （MIS） capacitors with Si02/HfO2//A12O3 stacked dielectrics are investigated for memory applications＇. A capacitance-voltage hysteresis memory window as large as 7.3 V is achieved for the gate voltage sweeping of ±12 V, and a fiat-band voltage shift of 1.5 V is observed in terms of programming under 5 V and I ms. Furthermore, the time- and voltage-dependent charge trapping characteristics are also demonstrated, the former is related to charge trapping saturation and the latter is ascribed to variable tunnelling barriers for electron injecting and discharging under different voltages.     

Improvement of Atomic-Layer-Deposited Al2O3/GaAs Interface Property by Sulfuration and NH3 Thermal Nitridation

Fermi level pinning at the interface between high-h gate dielectric and GaAs induced by unstable native oxides is a major obstacle for high performance GaAs-based metal-oxide-semiconductor （MOS） devices. We demonstrate the improved Al2O3/GaAs interracial characteristics by （NH4）2S immersion and NH3 thermal pretreatment prior to A1203 deposition. X-ray photoelectron spectroscopy （XPS） analysis confirms that sulfuration of GaAs surface by （NH4 ）2S solution can effectively reduce As-O bonds while Ga-O bonds and elemental As still exist at Al2O3 /GaAs interface. However, it is found that N incorporation during the further thermal nitridation on sulfurated GaAs can effectively suppress the native oxides and elemental As in the sequent deposition of Al2O3. Atomic force microscopy （AFM） shows that the further thermal nitridation on sulfurated GaAs surface can also improve the surface roughness.     

脊形掺铒Al2O3光波导放大器级联特性的模拟计算

利用有限元法分析了脊形掺铒Al₂O₃光波导放大器内信号光和抽运光的场模式分布、速率方程求解铒离子五能级系统的粒子数分布.数值模拟了光波导净增益与信号光功率的关系和多个放大器级联的净增益特性.结果表明：级联系统存在着净增益亏损.低掺铒浓度的光波导作前级放大器的组合方式,级联系统总净增益最大.     

GaN MOS-HEMT Using Ultra-Thin A1203 Dielectric Grown by Atomic Layer Deposition

We report a GaN metal-oxide-semiconductor high electron mobility transistor （MOS-HEMT） with atomic layer deposited （ALD） Al2O3 gate dielectric. Based on the previous work [Appl. Phys. Lett. 86 （2005） 063501] of Ye et al. by decreasing the thickness of the gate oxide to 3.5nm and optimizing the device fabrication process, the device with maximum transconductance of 150mS/mm is produced and discussed in comparison with the result of lOOmS/mm of Ye et al. The corresponding drain current density in the 0.8-μm-gate-length MOS-HEMT is 800mA/mm at the gate bias of 3.0 V. The gate leakage is two orders of magnitude lower than that of the conventional A1GaN/GaN HEMT. The excellent characteristics of this novel MOS-HEMT device structure with ALD Al2O3 gate dielectric are presented.     

Sol-gel法制备Er3+-Yb3+共掺杂Al2O3粉末光致发光特性

采用异丙醇铝[Al(OC₃H₇)₃]为前驱体,溶胶-凝胶(Sol-gel)法制备Er³⁺-Yb³⁺共掺杂Al₂O₃粉末.实验结果表明:900 ℃烧结的粉末为固溶Er³⁺、Yb³⁺的γ-(Al,Er,Yb)₂O₃相和少量θ-(Al,Er,Yb)₂O₃相的混合物.Er³⁺-Yb³⁺共掺杂Al₂O₃粉末具有中心波长为1.533 μm的光致发光(PL)特性.1 mol % Er³⁺和1 mol% Yb³⁺共掺杂的Al₂O₃粉末的PL强度较1 mol % Er³⁺掺杂提高2倍,半峰宽从53 nm增加到63 nm.随泵浦功率的提高,PL强度呈线性增加后渐呈饱和趋势.     

Influence of oxygen pressure on structural and optical properties of Al2O3 optical waveguides prepared by pulsed laser deposition

Pure and europium doped alumina waveguides have been prepared by Pulsed Laser Deposition using a KrF excimer laser at oxygen pressures in the range from 10^-7 to 0.1 mbar. The composition of the films and the doping ion concentration were determined by Rutherford Backscattering Spectroscopy. From X-ray diffraction measurements, a progressive growth of %-Al₂O₃ crystallites is observed as the oxygen pressure decreases. After annealing treatment, the alumina films are constituted of !-Al₂O₃ crystallites while europium doped alumina films remain constituted of %-Al₂O₃ crystallites. The films have optical waveguiding properties. The mean refractive index of the film increases as oxygen pressure decreases.