Molecular dynamics simulations of La_2O_3 thin films on SiO_2

Classical molecular dynamics is used to investigate the equilibrium state of the surface region and interface of heteroepitaxial La_2O_3 thin films.Due to the lattice mismatch,heteroepitaxial thin films are subject to very large stress.For this reason the behavior of La_2O_3 thin films at SiO_2interface becomes an important concern.Our result indicates that La_2O_3 can uniformly wet SiO_2 surface.The properties of the simulated films are analyzed and the lack of any discernible crystalline phase in epitaxial La_2O_3 on SiO_2 indicates that the lattice mismatch between SiO_2 and La_2O_3 is sufficiently large to prevent the formation of even short-range orders in La_2O_3 film.     

低镍甲烷化催化剂中镍和氧化镧的分散研究

本文用X射线衍射法(XRD), 透射电镜(TEM), 配合电子衍射对Ni/Al2O3,Ni/γ-Al_2O_3-La_2O_3等催化剂中镍晶粒度和La_2O_3的分散状态进行了测量和讨论。用透射电镜测量了不同La_2O_3含量的催化剂中镍晶粒度分布, 其平均直径可与X射线宽化法测定值相比较。催化剂中随La_2O_3加入量的增加, Ni晶粒有细化趋势, 从而提高了甲烷化催化活性。对La_2O_3在γ-Al_2O_3表面作密置单层分散的模型提出了新的旁证, 并推断由于La_2O_3在γ-Al_2O_3表面高分散并产生较强相互作用, 使γ-Al_2O_3接近表层晶格发生畸变。     

Li／La2O3的表面活性氧及其在甲烷氧化偶联中的催化行为

甲烷氧化偶联反应近年来研究十分活跃。Lunsford等报道了载有碱金属的碱土氧化物是对此反应有效的催化剂,并提出晶格取代型活性中心[M~ O~-〕和表面活化、气相偶联的反应机理。Otsuka等系统地研究了稀土氧化物的甲烷氧化偶联活性,本文通过氧化镧中添加锂前后的对比,运用骤冷技术与ESR法研究了催化剂的表面活性氧,以低温TPD法研究了甲烷在催化剂表面上的吸附与活化,以及在甲烷氧化偶联中的催化行为。     

层状光催化材料H2La2Ti3O10/CdS的制备及其性质研究

通过改善酸交换过程,用分步柱撑法制备了一种新的层柱材料H2La2Ti3O10/CdS.用X射线粉末衍射（XRD）、红外光谱（IR）、比表面（BET）等方法对材料进行了表征;以光催化降解苯胺为探针对材料的活性进行了研究.结果表明： 通过柱撑CdS,H2La2Ti3O10的光催化性能得到明显提高;同时,对试验条件进行了优化,得到了最佳催化反应条件.     

CO2氧化丙烷脱氢MoO3-V2O5/SiO2催化剂研究

采用表面改性和等体积浸渍法制备了MoO3-V2O5／SiO2复合氧化物，采用TPR、IR、TPD和微反技术表征了催化剂对CO2和C3H8的吸附性能和CO2部分氧化丙烷脱氢的反应性能．结果表明：随MoO3加入量的增加，V=O还原温度降低，晶格氧更易活化．CO2和丙烷的活化温度降低，丙烷转化率增高，丙烯选择性下降．V=O中晶格氧的活化是CO2氧化丙烷制丙烯反应的关键．     

La2O3掺杂TiO2光催化剂的制备和性能

采用溶胶-凝胶法制备了La2O3掺杂TiO2纳米光催化剂，并通过XRD、TEM、BET和XPS等手段进行了表征．掺入La2O3后，阻止了TiO2从锐钛矿晶型向金红石晶型的转变，使TiO2的粒径减小，比表面积增大．以甲基橙为光催化降解反应模型化合物，考察了光催化剂的活性．测定了甲基橙在纯TiO2和La2O3掺杂TiO2光催化剂上的吸附常数．考察了pH、H2O2对降解性能的影响．讨论了光催化活性与催化剂性质的关系．     

Cerium-modified Ni-La_2O_3/ZrO_2 for CO_2 methanation

The key point in CO_2 methanation is to improve the activity at low temperature and the stability.For this purpose,a new cerium-modified Ni-La_2O_3/ZrO_2 catalyst was prepared using La_(1-x)Ce_xNiO_3/ZrO_2 with perovskite phase as the precursor,which was obtained by citrate complexation combined with an impregnation method.The resulting catalyst was characterized through Nitrogen adsorption and desorption,X-ray diffraction (XRD),Transmission electron microscopy (TEM),Hydrogen temperature programmed reduction (H_2-)TPR),Temperature-programmed desorption of CO_2 (CO_2-TPD) and that of H_2 (H_2-TPD),and X-ray photoelectron spectroscopy (XPS) techniques,and the catalytic performances for CO_2 methanation was investigated.Cerium modification could improve the effective activation of CO_2,thus enhancing the activity at low temperature for CO_2 methanation.The metal Ni nanoparticles prepared using this method were highly dispersed and showed excellent resistance to sintering,leading to very good stability,which could be attributed to the following:Ni nanoparticles could be confined by cerium-modified La_2O_3;La_2O_3could be confined by the cerium ions at the La_2O_3/ZrO_2 interface;and the cerium ions were confined by ZrO_2.     

掺杂物对负载型ZrO_2/Al_2O_3的催化性能的影响

用浸渍-沉淀法分别制备了负载型ZrO_2/Al_2O_3和ZrO_2-(MgO、 K2O、 CeO_2、La_2O_3)/Al_2O_3催化剂. 用XRD、 BET、 TPD对催化剂的晶相结构、比表面积、孔径分布、表面酸碱性等进行了表征;同时以CO_2和CH_3OH为探针用原位红外对催化剂的吸附行为进行研究. 结果表明, 掺杂氧化物有效的阻止ZrO_2晶粒的团聚, 并提高了催化剂的比表面积和平均孔径;CeO_2的添加有利于碱性中心数的增多, La_2O_3有利于酸性中心数的提高. 原位红外结果表明CH_3OH能在ZrO_2-(CeO_2、 La_2O_3)/Al_2O_3催化剂表面发生解离吸附, 而CO_2在催化剂表面均出现单齿态吸附. CO_2和CH_3OH在常压下直接合成碳酸二甲酯(DMC)反应中ZrO_2-(CeO_2、 La_2O_3)/Al_2O_3催化剂表现出较好的催化活性和选择性.     

Cr2O3-Co3O4／SiO2对十八醇氧化生成十八酸反应的催化性能

 制备了一系列不同Cr／Co比例的Cr2O3－Co3O4／SiO2催化剂，并用XRD，FT－IR和BET等手段对催化剂进行了表征；考察了催化剂对十八醇氧化生成十八酸反应的催化性能，及反应条件（反应温度和反应时间）对催化性能的影响，确定了最佳反应条件．结果表明，金属硝酸盐在773K焙烧后转变成相应的氧化物并负载于二氧化硅上．Cr2O3－Co3O4／SiO2催化剂对十八醇氧化反应有很高的催化活性，十八酸选择性最高可达99．93％，收率可达52．44％．Cr2O3－Co3O4／SiO2催化剂的活性明显高于单一的Cr2O3／SiO2或Co3O4／SiO2催化剂     

La2O3对Pd/Al2O3催化蒽醌氢化制H2O2性能的影响

 采用湿浸法制备了用于蒽醌氢化制H2O2的La2O3促进的Pd/Al2O3催化剂,并考察了不同La2O3含量对催化性能的影响. 采用XRD,N2物理吸附,CO2-TPD,H2-O2滴定和电子探针等技术对催化剂进行了表征. 结果表明,加入适量的La2O3能够抑制高温焙烧时Al2O3晶粒的长大,增大催化剂的比表面积,提高金属Pd的分散度,增强载体表面碱性,提高催化剂表面的Pd浓度,减小Pd层厚度,从而提高催化剂的氢化活性. 加入La2O3可使催化剂的Pd负载量由0.281%降至0.188%,而催化剂活性提高了44%.     

Ca2+xLa8-x(SiO4)6O2-0.5x的合成及其导电机理

Ca2+xLa8-x(SiO4)6O2-0.5x的合成及其导电机理;溶胶凝胶法;硅酸盐氧基磷灰石;空位导电机理;电化学阻抗谱     

金属氧化物改性的HZSM-5上甲苯与甲醇的烷基化反应

 考察了La2O3,MgO以及La2O3-MgO复合改性的HZSM-5催化剂的孔结构、表面酸性和吸附性能,以及它们在甲苯与甲醇烷基化反应中的催化性能. 未经改性的HZSM-5上甲苯甲基化反应产物组成为热力学平衡组成,而改性后的催化剂上目标产物对二甲苯选择性提高,但反应活性下降. La2O3改性使HZSM-5孔径缩小,孔道变窄,强酸和弱酸酸量均降低,目标产物选择性明显提高; MgO主要分布在沸石外表面和孔口,因而MgO改性的HZSM-5孔口尺寸稍有缩小,另外强酸酸量减少,弱酸酸量略有上升,对二甲苯选择性略有提高; 而La2O3-MgO复合改性的催化剂上对二甲苯选择性显著提高,达到93%. 结果表明,反应的对位选择性是孔径和表面酸性同时调变的结果,孔径效应比酸性分布对催化剂的对位选择性影响更大.     

烧绿石结构La2Ti2-xCoxO7的制备及可见光分解水性能

采用溶胶-凝胶法制备了烧绿石结构的光催化剂La2Ti2-xCoxO7 (x=0, 0.05, 0.10, 0.20), 通过XRD、FT-IR、BET、UV-Vis漫反射光谱等测试手段对催化剂的晶体结构、比表面积以及漫反射光谱进行了表征, 采用光催化反应装置和气相色谱仪对产氢速率进行了测定.研究结果表明, La2Ti2O7只在紫外光下有吸收, 而Co对La2Ti2O7的B位掺杂能使其在可见光区有明显的吸收; La2Ti2O7的Co掺杂不仅提高了其在紫外光照射下分解水制氢的能力, 而且可使其在可见光照射下分解水制氢; 在La2Ti2-xCoxO7(x=0-0.20)系列中, La2Ti1.9Co0.1O7分解水制氢能力最强.     

In-Situ FT-IR Investigation of Partial Oxidation of Methane to Syngas over Rh/SiO_2 Catalyst

Partial oxidation of methane to syngas(POM)over Rh/SiO_2 catalyst was investigated using in-situ FT-IR.When methane interacted with 1.0wt%Rh/SiO_2 catalyst,it was dissociated to adsorbed hydrogen and CH_x species.The adsorbed hydrogen atoms were transferred to SiO_2 surface by"spill-over"and reacted with lattice oxygen to form surface -OH species. POM mechanism was investigated over Rh/SiO_2 catalyst using in-situ FT-IR.It was found that CO_2 was formed before CO could be detected when CH_4 and O_2 were introduced over the preoxidized Rh/SiO_2 catalyst,whereas CO was detected before CO_2 was formed over the prereduced Rh/SiO_2 catalyst.     

CrO3在γ-Al2O3和SiO2载体表面的分散状态

用X光衍射(XRD)方法研究了CrO_3/SiO_2和CrO_3/γ-Al_2O_3体系。用相定量外推法测定活性组份在载体表面的最大分散量。在干燥气氛中将CrO_3与载体混合, 并在低于CrO_3熔点的温度下烘烤制备样品, 实验得到CrO_3在SiO_2或者γ-Al_2O_3表面的最大分散量都随温度的升高而增大。CrO_3在SiO_2表面的最大分散量由101 ℃的0.27gCrO_3/g SiO_2到170 ℃的0.38g CrO_3/g SiO_2; CrO_3在γ-Al_2O_3表面的最大分散量由120 ℃的0.22g CrO_3/g γ-Al_2O_3到171 ℃的0.42g CrO_3/g γ-Al_2O_3。CrO_3在SiO_2或γ-Al_2O_3表面的最大分散量超过密置单层量, 可由易聚合形成同多酸根来解释。     

TiO2薄膜的Ag改性及光催化活性

 用光化学沉积法对纳米TiO2薄膜进行了Ag改性,用漫反射紫外-可见光谱、扫描电子显微镜和X射线光电子能谱分析了Ag-TiO2薄膜的光谱特征、表面形貌和表面组成. 以苯酚为模拟污染物,在不同波长光源及有氧和无氧条件下考察了Ag-TiO2薄膜的光催化活性. 结果表明,当银沉积量大于 0.0150 mg/cm2时, Ag-TiO2薄膜对紫外光的吸收发生了明显的蓝移,同时在346 nm附近出现了小的吸收峰且该峰随着银沉积量的增加逐渐向长波方向移动. 沉积在TiO2薄膜表面的银颗粒大小不均匀,主要以单质银的形式存在,也生成了部分Ag2O; 相对于TiO2薄膜, Ag-TiO2薄膜表面吸附氧的含量明显增大. Ag-TiO2薄膜的光吸收特性对其催化活性影响较大. 在低压汞灯及有氧参与的条件下,银沉积量为0.0523 mg/cm2的Ag-TiO2薄膜的催化活性最高, 其反应速率常数是TiO2薄膜的1.16倍. Ag+更易沉积在较大n值的Ag簇上,其颗粒大小不可能完全均匀. Ag-TiO2薄膜的光吸收特性、 Ag簇的大小以及Ag对O2的吸附作用是决定Ag-TiO2薄膜催化活性的主要因素.     

Study of the Interface Microstructures of CVD Diamond Films by TEM

 The characteristics of the interface microstructures between a CVD diamond film and the silicon substrate have been studied by transmission electron microscopy and electron energy loss spectroscopy. The investigations are performed on plan-view TEM specimens which were intentionally thinned only from the film surface side allowing the overall microstructural features of the interface to be studied. A prominent interfacial layer with amorphous-like features has been directly observed for CVD diamond films that shows a highly twinned defective diamond surface morphology. Similar interfacial layers have also been observed on films with a <100> growth texture but having the {100} crystal faces randomly oriented on the silicon substrate. These interfacial layers have been unambiguously identified as diamond phase carbon by both electron diffraction and electron energy loss spectroscopy. For the CVD diamond films that exhibit heteroepitaxial growth features, with the {100} crystal faces aligned crystallographically on the silicon substrate, such an interfacial layer was not observed. This is consistent with the expectation that the epitaxial growth of CVD diamond films requires diamond crystals to directly nucleate and grow on the substrate surface or on an epitaxial interface layer that has a small lattice misfit to both the substrate and the thin film material.     

二氧化钛薄膜的低温制备及其性能表征

通过水煮法在较低温度下制备了均匀、透明的TiO2-SiO2复合薄膜,利用XRD、AFM和UV-Vis光谱等手段对薄膜的物相、表面形态结构和透明性进行了表征,分析了SiO2的添加对薄膜性质的影响.并利用紫外光照降解罗丹明B溶液评价了薄膜的光催化活性及其影响因素.实验结果表明,通过水煮法在较低温度下制备的薄膜具有较高的光催化活性,适量SiO2的添加能够提高薄膜的光催化活性.     

V2O5在硅胶表面的分散及助剂K2SO4作用的研究

用原位XRD方法证明V_2O_5能在硅胶表面自发分散, 但所需温度较高. 水汽对V_2O_5的分散有一定的阻碍作用. K_2SO_4可显著加快V_2O_5在SiO_2表面的分散速度, 并能降低V_2O_5/SiO_2的表面酸性. 被中和的主要是强酸位. 这可能是K_2SO_4能够改善V_2O_5/SiO_2催化剂在选择氧化反应中选择性的重要原因之一.     

Enhancement of H2 Sensing Properties of In2O3-based Gas Sensor by Chemical Modification with SiO2

The sensitivity and selectivity to H2 of a new In203-based gas sensor were improved significantly by surface chemical modification. A dense layer of SiO2 near the surface of the porous In2O3 bead was formed by chemical vapor deposition (CVD) of diethoxydimethysilane (DEMS). The dense layer functioned as a molecular sieve, thereby the diffusion of gases with large molecular diameters, except for 1-12, was effectively controlled, resulting in a prominent selectivity and high sensitivity for H2. The working mechanism of the sensor was also presented.