Nanoraspberry-like palladium/spongy nickel oxide for electrooxidation of five light fuels

The spongy nickel oxide (SNO) was synthesized the solution combustion method. The SNO was selected as a promoter to boost the catalytic activity of nanoraspberry-like palladium (NRPd) toward electrooxidation of five light fuels (LFs): methanol, ethanol, formaldehyde, formic acid, and ethylene glycol. The X-ray powder diffraction, Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy, and field emission scanning electron microscope techniques were used for the materials characterization. In comparison with nonpromoted Pd, the NRPd-SNO electrocatalyst shown an excellent efficiency in parameters like the electrochemical active surface area and anti-CO poisoning behavior. The turnover data and the parameters, including reaction order, activation energy, and the coefficients of electron transfer and diffusion, were evaluated for the each process of LFs electrooxidation. The outcome for NRPd-SNO activity toward LFs electrooxidation was compared to some reported electrodes. The SNO increases the removal of intermediates created in the oxidation of LFs that can poison the surface of palladium catalyst. This is due to the presence of the lattice oxygens in SNO structure and Ni switching between its high and low valances. The compatibility of the adsorption process of LFs on the surface of the NRPd-SNO catalyst with different isotherms was determined by studying the Tafel polarization and calculating the surface coverage.     

电感耦合等离子体原子发射光谱法测定辛酸铑催化剂中铂钯铅铁铜铝镍

准确测定辛酸铑催化剂中杂质元素含量,是判定产品是否合格的重要指标之一。以往常采用直流电弧发射光谱法(摄谱法)进行检测,但测定周期长,且重复性较差。用电感耦合等离子体原子发射光谱法(ICP-AES)测定辛酸铑催化剂中微量杂质元素时,辛酸铑催化剂样品中含有的大量有机组分和铑基体会对测定有严重干扰。实验采用反复滴加硝酸消解样品中有机组分,再用王水溶解盐类,选用合适背景点扣除的方式消除铑基体的干扰,建立了使用ICP-AES测定辛酸铑催化剂中0.001%~0.1%(质量分数)Pt、Pd、Pb、Fe、Cu、Al、Ni等7种微量杂质元素的方法。各元素在0.10~10.00μg/mL范围内与其发射强度呈线性关系,相关系数均大于0.9999;方法检出限(μg/mL)为0.075(Pt)、0.0033(Pd)、0.015(Pb)、0.0036(Fe)、0.010(Cu)、0.001(Al)、0.012(Ni)。实验方法用于测定辛酸铑催化剂样品中Pt、Pd、Pb、Fe、Cu、Al、Ni,结果的相对标准偏差为(RSD,n=7)为1.4%~9.6%。按照实验方法测定辛酸铑催化剂中Pt、Pd、Pb、Fe、Cu、Al、Ni,并与直流电弧发射光谱法的测定结果进行比对,结果相一致。     

Coating the porous Al2O3 substrate with a natural mineral of Nontronite-15A for fabrication of hydrogen-permeable palladium membranes

Substrate surface modification is a key pretreatment during fabrication of composite palladium membranes for hydrogen purification in hydrogen energy applications. The suspension of a natural porous material, Nontronite-15A mineral, without any organic additives was employed in dip-coating of the porous Al₂O₃ substrate. The Nontronite-15A mineral was characterized by SEM, XRD, TG−DSC and granulometry analysis. The surface and cross-section of the coated porous Al₂O₃ tubes were observed by SEM, and their pore size distribution and nitrogen flux were also measured. Palladium membranes were fabricated over the coated Al₂O₃ tubes by a suction-assisted electroless plating. The optimal loading amount of the Nontronite-15A mineral is just to fill in and level up the surface cavities of the Al₂O₃ substrate rather than to form an extra continuous layer. A thin and selective palladium membrane was successfully obtained, and its permeation performances were tested. The kinetic analyses on the hydrogen flux indicate that the hydrogen permeation behavior exhibits typical characteristics for most of the palladium membranes. During the stability test at 450 °C for 192 h, no membrane damage was detected, and the hydrogen flux increased slightly.     

Pd-Decorated Tungsten as Pt-Free Bimetallic Catalysts for Hydrogen Oxidation Reaction in Alkaline Electrolyte

Developing Pt-free catalysts for hydrogen oxidation reaction (HOR) in alkaline solution is becoming a key challenge in the development of anion exchange membrane fuel cells and electrochemical reactors. Herein, we present the preparation, HOR activity, and stability of Pd-decorated tungsten (Pd-d-W) catalysts. The Pd-d-W catalysts were prepared by the chemically activated surface of tungsten nanoparticles by Pd ions. The resultant bimetallic catalysts consisted of crystalline phases of both Pd and W nanoparticles. The CO stripping voltammograms and H-desorption (H_des) peak potential of hydrogen desorption in Pd suggests that the enhancement of HOR catalytic activity observed in Pd-d-W catalyst can be ascribed to the modification of electronic property of Pd and availability of OH_ad near-surface Pd atoms.     

铂钯精矿中氯化银的浸出预处理研究

铜阳极泥分铜液所得铂钯精矿中的银主要以氯化银(AgCl)形态存在，可用氨水或亚硫酸钠作为浸出剂去除银。绘制了Ag⁺与NH3、SO2- 3配体组分图，结合电位-pH图分析表明，氨浸的pH值范围为7.7~13.5，亚硫酸钠浸出宜在中性或碱性条件下进行。优化条件实验结果表明，银的氨浸浸出率为95.3%，碲浸出率为14.9%，有微量铂、钯浸出；以亚硫酸钠为浸出剂，银的浸出率为97.3%，碲浸出率为11.5%，金、铂和钯均不被浸出。亚硫酸钠更适于作为铂钯精矿预处理除银的浸出剂。     

Electrosynthesis of dendritic palladium supported on Ti/TiO2NTs/Ni/CeO2 as high-performing and stable anode electrocatalyst for methanol electrooxidation

Liquid-fueled direct methanol fuel cell (DMFC) is highly promising for low-carbon transportation, but is hindered by high cost and short lifespan of conventional Pt-based electrocatalysts. Herein, we propose a new Pt-free catalyst strategy to exploit high-performing and stable electrocatalyst of DMFC, achieving enhanced electrocatalytic activity and high stability for methanol oxidation reaction (MOR) in alkaline media. A new Pt-free anode catalysts consisting of titanium/reduced-titanium dioxide nanotubes/nickel/cerium dioxide (Ti/r-TiO₂NTs/Ni/CeO₂) nanosupport and uniformly-dispersed Pd dendrites is successfully prepared by a facile three-step electrodeposition route without applying any template or surfactant. Noticeably, the as-prepared Ti/r-TiO₂NTs/Ni/CeO₂–Pd as an anode electrode exhibits superior activity than commercial Pd/C and other electrodes. The obtained large mass activity for Ti/r-TiO₂NTs/Ni/CeO₂–Pd electrode is 1752 mA mg_Pd^?1 for MOR. After successive CV tests of 1000 cycles, Ti/r-TiO₂NTs/Ni/CeO₂–Pd electrode still retained 88.9% of its initial current. The superior performance of Ti/r-TiO₂NTs/Ni/CeO₂–Pd attributes to the large surface area and excellent conductivity, as well as the synergistic effects among nanosupport and Pd dendrites. Therefore, this study will open a new door for high-performance fuel cell applications.     

连续流中介孔二氧化钛负载钯催化Suzuki偶联反应（急）

以氯化钯和钛酸正丁酯为原料，聚乙烯吡咯烷酮为金属保护剂，三嵌段共聚物F127为模板剂，采用溶胶凝胶法制备了钯负载量为0.1 wt%~1.0 wt%的非均相 Pd/m-TiO2催化剂。经BET、XRD和TEM表征,催化剂具有有序介孔结构，孔径分布在8 nm~10 nm，钯金属颗粒均匀分散在载体上，颗粒尺寸为11.3 nm~13.3 nm。在微填充床反应器中进行了连续流Pd/m-TiO2催化Suzuki偶联反应研究，确定了最优工艺条件：混合溶剂N,N-二甲基甲酰胺（DMF）和水（V:V=1:1，400 mL），碱为磷酸钾（n碱:n溴苯=1.5:1），流速为0.20 mL/min，溴苯、苯硼酸和磷酸钾的浓度分别为0.10 mol/L、0.12 mol/L和0.15 mol/L，钯负载量为0.7 wt%，反应温度为80 ℃，6.8 min反应时间内Suzuki偶联反应收率达99%，催化剂重复使用多次后仍保持良好催化活性。     

钯催化Suzuki偶联反应的研究进展

金属Pd催化的Suzuki偶联反应是碳-碳偶联反应中重要的反应之一。综述了近年来Pd催化Suzuki偶联反应的研究进展,其中包括Suzuki反应机理、配体种类及其在有机合成中的应用。介绍了含N、P配体的钯催化剂和碳纳米管、磁性材料、多孔材料、水滑石、金属氧化物、高分子材料等负载的无配体钯催化剂的研究进展。     

Mathematical modeling of the partial hydrogenation of vegetable oil in a monolithic stirrer reactor

Experimental and theoretical studies on the partial hydrogenation of vegetable oil in a monolithic stirrer reactor are reported. A complete mathematical model of the reactor was developed, including hydrogenation and isomerization kinetics, catalyst deactivation, external gas–liquid and liquid–solid as well as internal mass transfer. The experimental studies were carried out in a Pd/Al₂O₃/Al monolithic stirrer reactor, at a wide range of temperatures (353–373 K), pressures (414–552 kPa), and catalyst loadings (0.00084–0.00527 kg_Pd,exp m^?3). Based on this model, simulated data can be used to evaluate the catalyst (Pd/Al₂O₃/Al) and the hydrogenation process in consecutive catalytic tests under different operating conditions. © 2014 American Institute of Chemical Engineers AIChE J, 60: 3524–3533, 2014