Pdx-Co/C催化甲酸的电氧化性能研究

以活性碳(Vulcan XC-72)为载体,用化学还原法制备了不同Pd/Co摩尔比的Pdx-Co/C催化剂。用透射电镜(TEM)、X射线衍射(XRD)及X射线光电子能谱(XPS)对催化剂进行了表征,采用循环伏安法考察了催化剂对甲酸电氧化反应的催化性能。结果表明,Pdx-Co复合催化剂粒子均匀分散在碳载体表面;催化剂中掺入的少量Co元素部分进入Pd晶格,形成了Pd-Co合金;随着Pd/Co摩尔比的增加,Pd颗粒粒径先增大后减小,催化活性也表现出相同的变化趋势;当Pd:Co=8:1时,所得Pd8-Co/C对甲酸氧化的催化活性最高,峰电流密度可达到15.907 mA/cm²。     

La-Pd负载工艺对单Pd三元催化剂起燃性能的影响

通过Pd的预还原和La-Pd共浸渍工艺制备了不同单Pd三元催化剂。通过CO化学吸附、XRD、TEM、H_2-TPR和起燃测试等表征手段,综合考察了Pd/Al_2O_3体系下Pd的预还原和La-Pd共浸渍工艺对其起燃性能的影响。试验结果表明,模拟气氛老化后,La-Pd/Al_2O_3-R催化剂表现出了较高的CO/NO_x/HC起燃活性。这主要是因为贵金属Pd的预还原和La-Pd共浸渍工艺相结合有利于在老化过程中形成活性较高的PdO_x/Pd物质。     

La助剂对Pd-AL2O3催化C3H8氧化性能的研究

采用不同稀土La前驱体浸渍掺杂改性Pd/γ-Al2O3催化剂,利用多功能催化性能评价装置测试不同催化剂的C3H8催化氧化性能,并通过H2-TPR、XRD、XPS等手段对催化材料进行结构表征,结果表明：La能促进贵金属钯分散,增强钯与载体相互作用,稳定高活性Pd2+物种,从而提高了催化剂的C3H8催化氧化性能。在选用不同La前驱体改性的Pd/γ-Al2O3催化剂中,硝酸镧改性效果最佳,能更好地促进活性金属钯的分散和Pd2+高活性物种的稳定。相比Pd/γ-Al2O3,La改性催化剂均降低了C3H8和NO的反应转化温度。选用不同La前驱体对催化活性影响存在差异的主要原因是La前驱体添加而引起的金属-载体相互作用和活性贵金属钯的分散状态变化。     

Pd基础催化剂的性能对比

在催化剂中添加镧可抑制活性位的长大和PdO颗粒的分解,增强催化剂的催化活性和热稳定性.研究了老化前和老化后的Pd/CZ/La-Al2O3系列、Pd/La-Al2O3、Pd/CZ催化剂,Pd/CZ/La-Al2O3系列中Pd、CZ(Ce1-xZrxO2)、La-Al2O3材料添加顺序不同对催化剂涂层性能的影响.对于老化前和老化后的催化剂,Pd、CZ、La-Al2O3材料添加顺序对催化活性影响较小,Pd/W有利于CO转化,Pd/CZ有利于HC、NOx转化.通过XRD、XPS、化学吸附仪、BET表征证明了老化过程中发生了催化失活.     

高活性Pd-Fe催化剂对CO的低温氧化性能研究

用共沉淀法制得Pd-Fe催化剂,考察了煅烧温度、载体、金属担载量对CO低温催化氧化反应活性的影响。结果表明,负载在炭黑上的Pd-Fe催化剂经200℃和300℃煅烧,性能最佳,在室温下可将CO完全转化。采用透射电镜(TEM)、X射线光电子能谱(XPS)、X射线粉末衍射(XRD)和CO化学吸附表征发现,催化剂的高活性是由于Pd与Fe之间具有强相互作用,导致Pd向界面Fe3+(Fe2O3)进行电子转移,形成还原态的Fex+物种。Pd O和还原态的Fex+物种分别是吸附CO和O2的活性中心,成为CO氧化高活性的主要原因。     

绿色合成AMA反应中纳米Pd/C催化剂的失活和再生

在2-硝基-4-乙酰胺基苯甲醚(NMA)催化加氢合成2-氨基-4-乙酰胺基苯甲醚(AMA)反应中,规整纳米Pd/C催化剂表现出很好的催化活性和选择性。但Pd/C催化剂在反应的套用过程中表现出反应活性逐渐降低。通过XRD、BET、EDS、XPS等物性表征以及Na2S滴定法和原子吸收法测定Pd含量的研究表明,钯微晶的长大、钯流失、催化剂中毒等不是引起Pd/C催化剂失活的主要原因,而Pd/C催化剂表面金属钯活性位在反应后被2-氨基-4-乙酰胺基苯甲醚产物等有机物覆盖可能是导致其性能逐渐降低的关键。使用酸洗法可以去除反应后Pd/C催化剂表面覆盖的2-氨基-4-乙酰胺基苯甲醚等有机物,释放金属钯活性位,实现Pd/C催化剂的性能有较大程度的恢复;而其他方法对Pd/C催化剂活性恢复的效果不明显。     

不同载体对甲醇分解钯催化剂性能的影响

用浸渍法制备了Pd/γ-Al2O3和Pd/Ce0.65Zr0.35O22种甲醇分解催化剂。采用XRD,NH3-TPD(NH3-Temperature-Programmed Desorption),XPS及H2-TPR(H2-Temperature-Programmed-Redution)等手段对2种催化剂的结构和性能进行表征,并考察了催化剂上甲醇低温分解的活性。结果表明,Pd/Ce0.65Zr0.35O2催化剂具有较弱的表面酸性及良好的低温还原性能;XPS结果表明2种催化剂中的Pd均以氧化态形式存在,并且Pd在Ce0.65Zr0.35O2固溶体上呈高度分散状态,Pd与Ce间具有较强的相互作用。结合活性考察可知,Pd+的存在有利于甲醇的分解。Pd/Ce0.65Zr0.35O2催化剂具有高的催化活性,220℃时甲醇转化率接近100%。     

新鲜和老化Pd/Al_2O_3密偶催化剂上催化C_3H_8转化催化性能（英文）

采用等体积浸渍法制备了以改性氧化铝为载体材料的Pd/Al_2O_3密偶催化剂,并采用H_2程序升温还原(H_2-TPR),CO化学吸附和X射线光电子能谱(XPS)对催化剂进行了表征。在模拟尾气条件下对催化剂的总包反应及与C_3H_8相关的单反应活性进行了测试。结果表明,老化处理后活性PdO_x数量下降,并伴随有金属态Pd~0的产生。老化后,起燃温度(T_(50))和完全转化温度(T_(90))分别提高了76和64℃,即催化剂低温活性比高温活性下降明显。对比新鲜和老化催化剂上单反应活性,结果表明,老化后无水条件下有NO参与的反应的低温活性下降显著。老化处理过程突出了NO对低温活性的抑制作用和H_2O对高温活性的促进作用。     

Pd/γ-Al2O3催化剂上甲烷-氘化氢之间的氢氘交换性能研究

利用浸渍法制备了Pd/γ-Al2O3催化剂,采用X射线粉末衍射(XRD)、X光电子能谱(XPS)和程序升温还原(TPR)等物理化学手段对其进行了表征,并在固定床微型反应器上考察了其催化活性。实验结果表明,载体内部有Pd元素,Pd和载体γ-Al2O3发生了强相互作用。在对甲烷与氘化氢间的氢氘交换反应中,Pd/γ-Al2O3催化剂显示出较好的催化活性。     

负载型钴钼金属氮化物的制备及其表面化学研究

采用等体积浸渍法结合NH3程序升温氮化技术,制备了一系列γ-Al2O3负载的Co/Mo金属氮化物催化剂。利用XRD、H2-TPR-MS和H2-TPSR-MS等手段,考察了Co/Mo金属氮化物催化剂及其氧化物前驱体的结构与表面性质;探讨了活性组分不同浸渍顺序制备的单、双金属氮化物的结构与表面性质差异;以NH3分解为探针反应考察了不同催化剂的反应性能差别。结果表明,活性组分的浸渍方式对催化剂的表面性质有重要的影响,共浸渍法制备的Co/Mo双金属氮化物由于其氧化物前驱体表面形成了CoMoO4相,有利于Co3Mo3N的生成。在NH3分解反应中,共浸渍法制备的Co/Mo双金属氮化物(0.56mol.g-1.h-1)比单金属氮化物和分步浸渍法制备的双金属氮化物具有更高的催化活性。     

Structural, mechanical and corrosion properties of TiOxNy/ZrOxNy multilayer coatings

Results on the deposition and characterization of TiO_xN_y/ZrO_xN_y multilayers, with bilayer periods of 20 and 400 nm, are presented. The coatings were deposited on TiNiNb alloy substrates by the pulsed magnetron sputtering method. The elemental composition, hardness, adhesion and corrosion resistance of the coatings were analyzed.As resulted from the XPS analysis, the individual layers consisted of a mixture of titanium or zirconium oxynitrides and corresponding oxides. X-ray analysis revealed that the coatings were amorphous. Only slight differences between the microhardness and adhesion values of the coatings with small and large bilayer period Λ were found. The experiments also showed that the multilayered coatings improved the corrosion resistance of the uncoated alloy and reduced the amount of ion release in artificial body fluids.     

MOCVD growth and characterizations of BxAl1−xAs and BxAl1−x−yInyAs alloys

Zinc-blende B_xAl_1−xAs and B_xAl_1−x−yIn_yAs alloys have been grown on exactly oriented (0 0 1)GaAs substrates by low pressure metalorganic chemical vapor deposition (LP-MOCVD). The influence of susceptor coating, growth temperature and gas-phase boron mole fraction on boron incorporation into AlAs has been comprehensively investigated. It has been found that boron incorporation into AlAs could be enhanced and the optimal growth temperature range of B_xAl_1−xAs alloys changed from 580 °C to 610 °C when SiC-coated graphite susceptors were replaced by the non-coated ones. In this study, the maximum boron composition x of 2.8% was achieved for the pseudomorphically strained B_xAl_1−xAs alloys. AFM measurements show that RMS roughness of B_xAl_1−xAs alloys increased sharply with the increase of gas-phase boron mole fraction. Raman spectra of B_xAl_1−xAs alloys show a linear increase of the BAs shift with boron composition x. Based on BAlAs deposition, bulk B_xAl_1−x−yIn_yAs (x = 1.9%) quaternary alloy was grown lattice-matched to GaAs successfully. Moreover, 10-period BAlAs/GaAs and BAlInAs/GaAs MQW heterostructures were also demonstrated.     

生物医用NiTi形状记忆合金腐蚀研究进展

镍钛形状记忆合金(NiTi-SMA)具有较好的耐腐蚀和机械性能,在口腔和临床医学中有着大量而广泛的应用。NiTi-SMA腐蚀后释放Ni²⁺会引发细胞毒性和过敏反应,进一步提高NiTi-SMA的耐蚀性是目前生物医学材料领域发展的核心之一。本文对近年来国内外有关口腔医学和临床医学中常用NiTi-SMA的腐蚀研究现状进行了总结,同时也对NiTi-SMA增材制造及表面改性技术进行了评述,以期为开发高性能抗腐蚀生物医用NiTi-SMA提供一定的指导意义。     

Li掺杂Ba(Ti1/7Sn1/7Zr1/7Hf1/7Nb1/7Ga1/7Li(1/7-x))O3高熵陶瓷的制备及介电性能研究

近年来,在高熵合金基础上发展起来的高熵陶瓷逐渐引起了研究者的广泛关注,其出现为开发高性能的无机非金属材料提供了新的设计思路。本文采用固相法制备了BaMO3基钙钛矿型高熵陶瓷Ba(Ti1/7Sn1/7Zr1/7Hf1/7Nb1/7Ga1/7Li(1/7-x))O3 (x = 0, 2.3%, 5.3%, 8.3%, 11.3%),并研究了Li含量对高熵陶瓷物相结构、微观形貌及介电性能的影响。结果表明,Li含量对陶瓷结构的影响不大,陶瓷均保持立方钙钛矿结构,且无杂相产生;陶瓷的晶粒尺寸相对较均匀。当x = 0时,即B位七元等摩尔比Ba(Ti1/7Sn1/7Zr1/7Hf1/7Nb1/7Ga1/7Li1/7)O3高熵陶瓷,其介电常数达到了最大值2920 (@100 Hz),相较于已报道的不掺Li的六元高熵钙钛矿陶瓷Ba(Ti1/6Sn1/6Zr1/6Hf1/6Nb1/6Ga1/6)O3提升了近50倍。     

Ag/LaNixCo1-xO3触点材料的制备及电接触性能研究

本文运用溶胶-凝胶燃烧法合成了双钙钛矿型LaNixCo1-xO3(LNCO)纳米材料,利用粉末冶金和热挤压技术制备了相应的Ag/LNCO触点材料及元件样品。重点考察了不同Ni、Co含量对Ag/LNCO触点材料微观结构、物相组成、物理性能、力学性能及电寿命服役能力的影响,对其电弧侵蚀失效行为进行了研究,并与SnO2粉体增强Ag基触点材料进行对比。结果表明:溶胶凝胶法合成的LNCO纳米颗粒粒径为20-30 nm,经粉末冶金工艺制备的Ag/LaNi0.5Co0.5O3触点材料电学性能和电寿命都优于Ag/SnO2触点材料,其电阻率低至2.10 μΩ?cm,电寿命性能达到51287次。表明Ag/LaNi0.5Co0.5O3触点材料性能较佳,是一种可以取代Ag/CdO的新型触点材料。     

Hydrothermal synthesis of superconductors Ba1−xKxBiO3 and double perovskites Ba1−xKxBi1−yNayO3

Superconductors Ba_1−xK_xBiO₃ and body-centered double perovskites Ba_1−xK_xBi_1−yNa_yO₃ have been selectively synthesized by a facile hydrothermal route. The appropriate ratio and adding sequence of initial reagents, alkalinity, reaction temperature and time are the critical factors that influence the crystal growth of the compounds. The purity and homogeneity of the crystals were detected by the ICP, SEM, EDX and TEM studies. Magnetic measurements show that the superconducting transition temperatures T_C of Ba_1−xK_xBiO₃ decrease from 22 K (for x = 0.35) to 8 K (for x = 0.55) with increasing the K doping level.     

High strength and good ductility of casting Al-Cu alloy modified by PrxOy and LaxOy

A modified Al-Cu alloy with high tensile strength and ductility of about 574.0 MPa and 10.4%, respectively, was obtained by adding multiple rare earth oxides (Pr_xO_y and La_xO_y) as modifier. Compared with the unmodified Al-Cu alloy, the tensile strength and ductility of the modified sample were increased by 24.3% and 42.5%, respectively. The improvement both in the strength and ductility may attribute to the finer crystal grains and dendrites, more homogeneously distributed θ′ phase precipitates and the intermetallic compounds formed at the crystal grain boundaries as well as in the space of the dendrites.     

Magnetic phase diagrams of the TbRh2−xPdxPdxSi2 and TbRu2−xPdxSi2 systems

The a.c. susceptibility and high field magnetization on TbRh_2−xPd_xPd_xSi₂ and TbRu_2−xPd_xSi₂ compounds were investigated up to 140 kOe. The (T,x) magnetic phase diagrams were determined. For both systems, an increase in the Pd content causes a decrease in the Néel temperature and changes the magnetization curves.     

Si3N4/Ti/Cu/Ni/Cu/Ti/Si3N4二次部分瞬间液相连接强度

采用Ti/Cu／Ni中间层对Si3N4陶瓷进行二次部分瞬间液相(PTLP)连接，研究连接工艺参数对Si3N4／Ti/Cu／Ni连接强度的影响，同时研究了连接强度随试验温度的变化规律。结果表明，在该试验条件下，室温连接强度随着二次连接温度的提高和二次保温时间的延长而提高，改变连接工艺参数对Si3N4／Ti/Cu／Ni二次PTLP连接界面反应层厚度无明显影响；连接强度在试验温度400℃时达到最大，随后随试验温度升高，连接强度降低，但在800℃前，其高温强度具有很好的稳定性。     

Thermoelectric properties of Sn1−x−yTiySbxO2 ceramics

Thermoelectric properties of Sn_1−x−yTi_y Sb_xO₂ ceramics were investigated in detail. The addition of Sb into SnO₂ matrix increased the electric conductivity, σ. The increase in the σ value should be caused by the increase in the carrier concentration. The Seebeck coefficients of all the samples were negative, which means that these samples have n-type conduction. The samples of this study have porous structure. The maximum Z value of all the samples measured in this study was 2.4 × 10⁻⁵ K⁻¹.