温度对电沉积制备Pt-Ni阴极催化剂性能的影响

采用电化学还原法在碳布上电沉积Pt-Ni合金催化剂作为质子交换膜燃料电池阴极。通过循环伏安线性扫描法确定Pt-Ni合金的沉积电位,并在该电位下考察了不同电解液温度下所得催化剂的物理、化学性质及电催化性能。研究表明:在-0.35 V电位下可得到Pt-Ni合金,不同的电解液温度会影响Pt-Ni合金催化剂结构、形貌及组分比,进而影响其催化性能。当电解液温度为50℃时,Pt-Ni合金催化剂具有最佳的催化活性,此时催化剂为较小的球状颗粒,Pt与Ni的原子比接近3∶1,其电化学活性表面积为44.19 m2/g,是电解液温度为70℃下制备的催化剂的1.8倍。适当的温度下电沉积制得的Pt-Ni合金催化剂明显提高了铂对氧还原的催化活性。     

Controlled synthesis and properties of palladium nanoparticles

In our research, the preparation processes of Pd nanoparticles (Pd NPs) with different methods by adding a certain amount of silver nitrate, iron chloride or sodium iodide are presented in order to control their size and morphology. Various sizes and shapes of Pd NPs are observed by alcohol reduction. The results show the size and morphology control of Pd NPs with chemical reductions of Pd salts by ethanol and ethylene glycol (EG) that have very different reduction processes. The modified polyol method with the gradual addition of Pd and polyvinylpyrollidone precursors in EG at 160°C has led to control their size and morphology in the 10?nm range using 0.02?M AgNO₃. It is observed that the Pd nanorod is also formed. The main factors that will control the shapes of Pd NPs have been presented to explain their growth and formation mechanisms in a control process.     

Formation and characterization of diamond crystals synthesized by microwave plasma CVD system

Abstract

Diamond crystals have been successfully synthesized on (100) Si wafer using microwave plasma CVD. The growth was conditioned in a flowing system in which the parameters, such as CH₄/H₂ ratio, pressure, temperature and microwave power were varied. Cubo‐octahedra or tetrakaidecahedra are the equilibrium shape of diamond single crystals obtained under all conditions and are therefore the basic unit for the formation of polycrystalline diamond films, mostly through repetitive twinning and secondary growth of diamond crystals on {100} habit planes of cubo‐octahedra. Both X‐ray diffraction and Raman spectroscopy were used to facilitate the analysis of the diamond crystallinity and purity. These qualities are similar to those of natural diamonds.     

Carbon paste electrodes modified by Pt and Pt-Ni microparticles dispersed in polyindole film for electrocatalytic oxidation of methanol

Electrocatalytic activity of the Pt microparticles dispersed into polyindole (PIn) films obtained by electropolymerization on carbon paste electrodes (CPE) towards methanol oxidation in perchloric acid medium has been demonstrated and investigated using cyclic voltammetry, potentiodynamic polarization, chronoamperometry and impedance spectroscopic techniques. The results show that PIn films obtained on these electrodes serve as good host matrices for the dispersion of Pt microparticles and exhibit good catalytic activity towards the electrooxidation of methanol compared to bulk Pt and CPE modified with Pt. The morphology and composition of the modified and unmodified films were obtained using SEM and EDX techniques. The effect of scan rate, amount of Pt and concentration of methanol, on the activity of the electrode has been tested. The effect of alloying Pt with different amounts of Ni was studied and it was found that when the metals are deposited from a solution containing the metal salts in 1:1 ratio the activity towards methanol oxidation was significantly enhanced.     

铝酸钠溶液中钒酸盐的析出行为研究

以氧化铝生产流程中氢氧化铝的洗涤液为原料,研究了苛性碱浓度、反应温度及反应时间对溶液中钒酸盐析出情况的影响。结果表明,钒酸盐的析出率随苛性碱浓度的升高和反应时间的延长而增大,随反应温度的升高而减小。当铝酸钠溶液的苛性碱浓度为200g/L、反应温度为30℃、反应时间为72h时,溶液中的钒元素可减少60%以上。结晶析出的钒酸盐主要为钒酸钠和偏钒酸钠,其晶体结构为八面体。     

Decane reforming reaction over Pt,Ir, Pt-Ir and Pt-Ni bimetallic catalysts supported on Y-zeolite

Pt, Ir, Pt-Ir and Pt-Ni bimetallic catalysts supported on NaY- and HY-zeolite were examined as a catalyst for producing gasoline from n-decane via simultaneous reforming and cracking. The catalysts were prepared by calcining and reducing metal-ion-exchanged Y-zeolite with O₂ and H₂ at 300°C., respectively. Thus prepared catalysts were characterized by hydrogen chemisorption and temperature programmed desorption of ammonia. Pt-Ni/NaY and Pt-Ir/NaY bimetallic catalysts offered the improved activity maintenance compared to Pt/NaY monometallic catalyst. The catalysts supported on HY-zeolite showed higher selectivity toward C₅–C₇ and skeletal isomers of C₅–C₇- and C₈–C₁₀ than those of the catalysts supported on NaY-zeolite, which is a desired characteristic for increasing octane value of gasoline these days. However, deactivation with reaction time was much more pronounced on HY-zeolite-supported catalyst. When the catalyst was prcsulfided with H,S, the stability with time on stream was enhanced and the selectivity was quite different from that of the catalyst before presulfiding. The acidity of Y-zeolite and presulfiding of catalyst greatly influenced the activny, selectivity and stability of Pt, Ir, Pt-Ir and Pt-Ni bimetallic catalysts supported on Y-zeolite in n-decane reforming reaction.     

PTC型BaTiO3陶瓷的孪晶和孪晶界

用透射电镜和高分辨电镜观察研究了PTC型BaTiO_3陶瓷的孪晶和孪晶界结构,并提出了可能的{111}孪晶及孪晶界的原子结构模型。结果表明,{111}孪晶形成氧八面体共面的共格倾斜孪晶界,在孪晶界处可能存在一定量的A空位且原子密度要低于孪晶体内。同时还发现两种其它特征的孪晶现象。     

准八面体CBN单晶的合成研究

通过对原料、触媒及合成工艺的研究，采用国产DS-029B型六面顶压机在4．2—5．3GPa，1350。1470℃的范围内，从hBN-单质触媒体系中合成出近乎完美的黑色八面体和截角八面体立方氮化硼单晶体。确定了该种形态的CBN晶体的生长区域。CBN晶体的尺寸在100—400μm，峰值粒度为125—150μm。对所得的晶体进行考察，发现这种CBN晶体结晶形貌发育比较完整、棱角尖锐、晶粒饱满，并且有较高的抗压强度。上述结果表明所用的单质触媒具有使CBN晶体均匀生长的能力，是一种合成CBN晶体的有效触媒，该种CBN晶体具有较好的破碎强度。     

广义八面体理论研究综述

在真三轴应力状态下,根据不同材料的破坏(屈服)面特征,依次采用三组破坏面对正六面单元体进行截取,则可得到一系列八面单元体(特别是岩土),亦即广义八面体,并进而可派生出其他相应的单元体,而已知的等倾八面体和双剪理论中的正交八面体则是其中的2类特征过渡单元体,由此构成了一个广义八面体单元体系.而不同单元体上的应力,则可通过双剪应力、静水应力和应力Lode参数建立起内在联系,并可据此对应力状态进行划分.在这一理论体系中,若首先考虑中间主应力和静水应力效应的情况,则可探究材料的多轴强度模型及其演变规律;其次,可根据材料的弹塑性理论,探究材料的强度、变形的本构关系;第三,可通过对建立在偏平面上的屈服方程,探索其演化规律.由此可初步建立起广义八面体理论体系的架构.进一步可在此基础上开展更为广泛的包括材料的弹-塑-粘、损伤、疲劳和蠕变等性征的内在规律,从而建立起较为完善的广义八面体理论体系.