Hydrogen-induced metal-oxide interaction studied on noble metal model catalysts

Summary The effect of hydrogen reduction on the structure and catalytic properties of “thin film”and “inverse”model systems for supported metal catalysts is discussed. Thin film model catalysts were obtained by epitaxial growth of Pt and Rh nanoparticles on NaCl(001), which were coated with amorphous or crystalline supports of alumina, silica, titania, ceria and vanadia. Structural and morphological changes upon hydrogen reduction between 473 and 973 K were examined by high resolution electron microscopy. Metal-oxide interaction sets in at a specific reduction temperature and is characterized by an initial “wetting”stage, followed by alloy formation at increasing temperature, in the order VO_x< TiO_x< SiO₂< CeO_x< Al₂O₃. “Inverse”model systems were prepared by deposition of oxides on a metal substrate, e.g. VO_x/Rh and VO_x/Pd. Reduction of inverse systems at elevated temperature induces subsurface alloy formation. In contrast to common bimetallic surfaces, the stable subsurface alloys of V/Rh and V/Pd have a purely noble metal-terminated surface, with V positioned in near-surface layers. The uniform composition of the metallic surface layer excludes catalytic ensemble effects in favor of ligand effects. Activity and selectivity, e.g. for CO and CO₂methanation and for partial oxidation of ethene, are mainly controlled by the temperature of annealing or reduction. Reduction above 573 K turned out to be beneficial for the catalytic activity of the subsurface alloys, but not for the corresponding thin film systems which tend to deactivate viaparticle encapsulation.</o:p>     

Silica-supported PtSn alloy doped with Ga, In or, Tl: Characterization and catalytic behaviour in n-hexane dehydrogenation

Silica-supported trimetallic catalysts containing Pt, Sn and a group 13 metal (PtSnM, M=Ga, In, Tl) were prepared by consecutive impregnation steps from cis-[PtCl₂(PPh₃)₂] and chloride precursors. X-ray diffraction (XRD), transmission electron microscopy (TEM), selected-area electron diffraction (ED) and energy dispersive X-ray analysis (EDX) showed large platelet-like particles of PtSn_1−xM_x phases. PtSnGa catalyst with a Pt/(Sn+Ga) molar ratio of 1.72 showed a bimodal particle distribution and a Pt phase was identified. Differences in surface structures were also revealed by the performance of catalysts in the dehydrogenation of n-hexane. For PtSnIn and PtSnTl (Pt/(Sn+M) molar ratio of about 1) the dehydrogenation was favoured. In contrast, PtSnGa catalyst yielded hydrogenolysis products. Photoelectron spectra showed the Pt 4f_7/2 level at a binding energy of 70.0–71.8 eV in all cases. Moreover, the FT-IR spectra of chemisorbed CO on the PtSnGa showed a slight shift in the ν(CO) toward higher values with respect to the monometallic catalyst, pointing to an electronic effect in accordance with photoelectron spectroscopy.     

Electrochemical characterization of Ni–Fe alloy codeposition under MHD control

The nickel–iron alloy electrodeposition is affected by a superimposed magnetic field. Some previous papers [Msellak et al., Magnetohydrodynamics, 39:487–493, 2003 and Msellak et al., J Magn Magn Mat, 281:295–304, 2004] have exhibited some dramatic changes in iron amount and morphology of these deposits. As it is usual for a magnetic field up to 1 T, no charge transfer effect can be expected, and the observed modifications can be explained by the magnetohydrodynamic convection that controls the iron species flux during the electrochemical reaction. By electrochemical impedance spectroscopy and physical investigations (scanning electron microscopy, X-ray diffraction, and inductively coupled plasma), the reduction process is analyzed, the characteristic parameters of the mechanism are determined, and the magnetic field effects can be quantified. Contribution to special issue on “Magnetic field effects in Electrochemistry”.     

铝锡合金制氢技术研究

采用机械球磨法制备了铝锡系列合金. 水解制氢曲线和XRD结果表明, 添加剂(锌和氢化物)的加入和球磨时间的延长, 有利于金属铝和金属锡的均匀混合和活性一致. 常温下该系列合金与水反应迅速, 氢气产量高. 尤其是球磨10 h的Al-10%Sn-5%Zn-5%MgH2(质量分数)合金, 在10 min内水解反应结束, 氢气产量为785 mL/g, 水解速率为78.5 mL/(min·g).     

Ni-Co、Ni-Cu双金属合金催化剂用于CO甲烷化

以钙钛矿型复合氧化物LaNi_0.9Co_0.1O₃和LaNi_0.9Cu_0.1O₃为前驱体制备了Ni-Co/La₂O₃和Ni-Cu/La₂O₃双金属合金催化剂。结果表明,双金属合金催化剂中,各组分间相互稀释,具有较强的抗烧结性能;催化剂表面的积炭主要取决于CO在催化剂表面的吸附形态,Ni-Co双金属催化剂中,Co掺杂改变了CO在催化剂表面的吸附形式和吸附强度,使得Ni-Co双金属催化剂具有较强的抗积炭性能。Ni-Co双金属合金催化剂用于CO甲烷化反应时,显现出较好的活性、选择性和稳定性。     

基于激光干涉测试技术的分离式Hopkinson压杆实验测试系统

分离式Hopkinson压杆（SHPB）实验的传统测试技术是基于应变片的电测技术,测试结果的可靠性强烈依赖于应变片与杆之间粘贴质量,受到人为因素的影响较大。本文中采用基于多普勒频移原理的双探头全光纤激光干涉测速技术,以粒子速度为监测目标,借助应力波传播理论,换算成试件的应变和应力,从而建立了SHPB实验的非接触光学测试系统。针对韧性和脆性两类材料,分别提出了激光正入射和激光斜入射两种测试技术。再以铝合金和PZT陶瓷为例,通过与传统的应变片测试结果以及DIC测量结果的对比分析,验证了两种测试技术的有效性。与传统的应变片测试技术相比,新的激光干涉测试技术具有免标定、抗干扰、可靠性高等许多优点,有助于实现SHPB实验测试系统标准化。

     

基于J-C模型的镁合金MB2动静态拉伸破坏行为

为了研究不同应力状态和应变率条件下镁合金MB2的拉伸破坏行为,利用材料试验机和分离式Hopkinson拉杆(SHTB),对镁合金MB2的光滑及缺口圆柱试件进行了动静态拉伸加载;拟合得到了镁合金MB2的动静态拉伸本构关系,建立了其修正的Johnson-Cook失效破坏准则,并对不同试件的拉伸破坏行为进行了数值模拟;利用SEM对宏观破坏模式对应的微观损伤机理进行了分析。结果表明,随着应力三轴度的增加,镁合金MB2的等效破坏应变先增大后减小,宏观破坏模式由剪切转为正拉断,微观损伤机制由混合断裂转变为韧窝断裂;而随着应变率的增加,等效破坏应变不断减小,破坏模式不发生改变。Johnson-Cook本构关系和修正后的Johnson-Cook失效破坏准则能较好地拟合动态静态拉伸实验结果并预测不同试件的杯锥形破坏特征。

     

铜合金微塑性成形力学性能及其本构关系

对不同晶粒大小、不同特征尺寸的H62黄铜箔进行微拉伸实验,分析试样晶粒大小和特征尺寸对材料变形行为的影响.随着晶粒尺寸的减小,试样拉伸屈服应力逐渐增大,晶粒尺寸对屈服应力的影响满足Hall-Petch细晶强化关系;屈服强度随厚度的减小先减弱而后增强,随宽度的减小而增强;晶体塑性理论、表面层模型可以解释延伸率、抗拉强度随比表面积的增大而减小的现象.在实验数据的基础上通过修正双线性模型建立H62黄铜箔微塑性成形本构模型.     

激光沉积修复TA15合金的组织和力学性能

采用激光沉积修复方法对TA15槽损伤试样进行了修复试验,考察了修复试样的组织和力学特点,发现激光修复试样组织是由基材的双态组织经由热影响区过渡到修复区的网篮组织。修复区组织为粗大的原始柱状晶,晶粒内为/网篮组织,晶内片层取向随机, 宽0.4~0.5 m。分析了修复区和坡面存在熔合不良缺陷的原因,并给出了纠正措施。修复试样的室温静拉伸结果表明,试样的抗拉强度接近工业锻件水平,表明修复区与基材之间形成了致密冶金结合,但由于修复区粗大柱状晶组织,试样的冲击韧性比基材稍差。     

激光沉积修复BT20合金的显微组织和力学性能

针对BT20钛合金锻件当量孔损伤进行激光沉积修复试验,考察了修复试样的组织和力学特点。修复区与基材之间形成了致密冶金结合,Al,Zr,Mo,V合金元素由锻件基体到激光修复区均匀分布,无宏观偏析,硬度分布从基材到修复区依次提高。热影响区组织是由基材的双态组织过渡到网篮组织;修复区组织为粗大的原始柱状晶,晶粒内为/网篮组织,晶内片层取向随机, 宽0.4~0.5 m。修复过程中发现,激光加工工艺参数选择不当、坡度过大等原因会造成修复区组织形成气孔和熔合不良等缺陷,但是通过优化工艺参数可以获得无缺陷修复试样。修复试样的室温静拉伸结果表明,试样的抗拉强度接近锻件基体强度,但修复件的韧性比锻件稍有提高。