Analysis of H_2S Tolerance of Pd-Cu Alloy Hydrogen Separation Membranes

The presence of a limited amount of H2S in H2-rich feed adversely affects the Pd-Cu membrane permeation performance due to the sulphidization of the membrane surface. A theoretical model was proposed to predict the S-tolerant performance of the Pd-Cu membranes in presence of H2S under the industrial water-gas-shift(WGS) reaction conditions. The ideas of surface coverage and competitive adsorption thermodynamics of H2S and H2 on Pd-Cu surface were introduced in the model. The surface sulphidization of the Pd-Cu membranes mainly depended on the pressure ratio of H2S to H2, temperature and S-adsorbed surface coverage, i.e., the occurrence of sulphidization on the surface was not directly related with the bulk compositions and structures [body centered cubic and face centered cubic(bcc or fcc)] of Pd-Cu alloy membranes because of the surface segregation phenomena. The resulting equilibrium equations for the H2S adsorption/sulphidization reactions were solved to calculate the pressure ratio of H2S to H2 over a wide range of temperatures. A validation of the model was performed through a comparison between lots of literature data and the model calculations over a rather broad range of operating conditions. An extremely good agreement was obtained in the different cases, and thus, the model can serve to guide the development of S-resistant Pd alloy membrane materials for hydrogen separation.

In vitro and in vivo evaluations of Mg-Zn-Gd alloy membrane on guided bone regeneration for rabbit calvarial defect

To develop a biodegradable membrane with guided bone regeneration(GBR),a Mg-2.0Zn-1.0Gd alloy(wt.%,MZG)membrane with Ca-P coating was designed and fabricated in this study.The microstructure,hydrophilicity,in vitro degradation,cytotoxicity,antibacterial effect and in vivo regenerative performance for the membrane with and without Ca-P coating were evaluated.After coating,the membrane exhibited an enhance hydrophilicity and corrosion resistance,showed good in vitro cytocompatibility upon MC3T3E-1 cells,and exhibited excellent antibacterial effect against E.coli,Staphylococcus epidermis and Staphylococcus aureus,simultaneously.In vivo experiment using the rabbit calvarial defect model confirmed that Ca-P coated MZG membrane underwent progressive degradation without inflammatory reaction and significantly improved the new bone formation at both 1.5 and 3 months after the surgery.All the results strongly indicate that MZG with Ca-P coating have great potential for clinical application as GBR membranes.

Progress of Palladium Alloy Membranes in Hydrogen Energy

Palladium and palladium alloy membranes have attracted wide attention in hydrogen permeation areas for their excellent permeability, perm -selectivity and thermal stability. This paper review the principle of hydrogen permeation, type of alloys and the fabrication methods. At last, the progress and achievements on palladium alloy membranes by Northwest Institute for Non-Ferrous Metal Research are emphasized.

Preparation Methods and Properties of PdCu Alloy Membrane for Hydrogen Transition

Pd and Pd alloy membranes are of increasing interest for hydrogen separation and purification due to their good thermal stability, high permeability and perfect selectivity. PdCu alloy (60wt% Pd) membranes have similar hydrogen permeability compared with PdAg alloy; meanwhile, it is cheaper than PdAg alloy. Furthermore, it has been reported that PdCu membrane has better resistance to poisoning and deactivation by H 2 S impurity. This paper reviews the properties and manufacturing methods of PdCu alloy membrane, finally, introduced some achievement made by us on PdCu alloy membrane.

Electrochemical Study of Lincomycin on Au-PtNPs/nanoPAN/ Chitosan Nanocomposite Membrane and Its Determination in Injections

The Au-Pt alloy nanoparticles（Au-PtNPs） were electrochemically deposited on the surface of polyaniline nanotube（nanoPAN） and chitosan（CS） modified glassy carbon electrode（GCE）. The electrochemical behavior of lincomycin at Au-PtNPs/nanoPAN/CS modified GCE was investigated by cyclic voltammetry, linear sweep voltammetry and chronocoulometry. Cyclic voltammetric experiments show that lincomycin at the nanocomposite membrane modified electrode exhibited a pair of quasi-reversible redox peaks in pH=6.0 PBS. The membrane could accelerate the electron transfer of lincomycin on the electrode and significantly enhance the peak current. In a range of 3.0-100.0 mg/L, the reductive peak current of lincomycin at 0.42 V was linearly related to its concentration and the linear regression equation was ip,c=0.2703ρ-0.0042（ip, c： μA; ρ： mg/L; r=0.998, n=7） with a detection limit of 1.0 mg/L（S/N =3）. Compared with other methods, this method exhibited many advantages such as high sensitivity, selectivity, wide linear range and low detection limit. The method was used to determine the content of lincomycin in injections commercially available with satisfactory results. Some electrochemical parameters involved in the redox reaction of lincomycin, such as parameter of kinetic ha, standard rate constant ks and the number of H^＋, were also calculated.

Large-scale and high-quality III-nitride membranes through microcavity-assisted crack propagation by engineering tensile-stressed Ni layers

Epitaxially grown III-nitride alloys are tightly bonded materials with mixed covalent-ionic bonds.This tight bonding presents tremendous challenges in developing III-nitride membranes,even though semiconductor membranes can provide numerous advantages by removing thick,inflexible,and costly substrates.Herein,cavities with various sizes were introduced by overgrowing target layers,such as undoped GaN and green LEDs,on nanoporous templates prepared by electrochemical etching of n-type GaN.The large primary interfacial toughness was effectively reduced according to the design of the cavity density,and the overgrown target layers were then conveniently exfoliated by engineering tensile-stressed Ni layers.The resulting III-nitride membranes maintained high crystal quality even after exfoliation due to the use of GaN-based nanoporous templates with the same lattice constant.The microcavity-assisted crack propagation process developed for the current III-nitride membranes forms a universal process for developing various kinds of large-scale and high-quality semiconductor membranes.

Palladium-based Membrane Applications for Hydrogen Purification

It describes the purification of hydrogen isotopes, separation with the preparation of palladium-based membrane's technology, types, application, advantages and disadvantages of palladium in this article. Due to excellent comprehensive properties palladium composite membrane will become the future direction of development. At the same time it will develop preparation methods of the membrane support body with high mechanical strength and heat resistance and low-cost and palladium-based membrane. Also it will explore high service life and high transmittance of novel composite membrane.

Fabrication of anodized aluminum oxide membrane with nanometer pores

The pure aluminum and Al Mg Mn alloy were anodized in 4%, 10% and 18.5% phosphoric acid solution, respectively. As for pure Al, the maximum thickness of anodized aluminum oxide (AAO) membrane, 216 nm, is obtained by being anodized in 4% solution. Its average pore diameter is around 70 nm, and pore density exceeds 10 10 /cm 2. Under the same technology condition, the membrane thickness decreases with increment of electrolyte content. TEM images show that element Mg or Mn added into aluminum alloy can damage the integration of AAO membrane. During anodizing of aluminum, the formed oxide layer is amorphous. After being annealed at 600 ℃ for 24 h, it is still amorphous. However, when membrane is annealed at 930 ℃, the amorphous oxide begins to transform to γ Al 2O 3 .

Pd-Cu合金复合膜的制备及表征

采用无电化学镀技术制备了Pd-Cu合金复合薄膜。复合膜的初始基体是0．2pm等级的316L多孔不锈钢圆片（PSS），经过改性的（含Pd）溶胶-凝胶ZrO2成膜技术对PSS表面进行了修饰。修饰后的PSS表面首先进行无电镀金属Pd膜，然后在Pd膜表面再镀金属Cu膜。最后把具有双金属镀层的膜片在773K，H2气氛（101kPa）下保持5～10h进行退火热处理，通过金属间分子热扩散把不锈钢基体上的金属Pd膜和金属Cu膜合金化为均匀的Pd-Cu合金复合薄膜。XPS确定表面组成为Pd90Cu10（质量分数／％）合金薄膜，经过XRD分析结合确定为单相无序fcc结构；而Pd59Cu41合金膜是由平衡fcc相和有序bcc相组成。通过SEM观察到Pd90Cu10合金薄膜（厚度5 μm）表面存在一些针孔；而Pd59Cu41合金膜（厚度10μm）没有针孔存在，这种合金复合膜应该具有极高的透H2选择性。

化学镀—电镀结合法制备的Pd-Cu/Al_2O_3膜及其透氢行为

以多孔Al2O3为基体,先化学镀钯然后再电镀铜,最后进行合金化处理制备了一系列钯铜合金膜。通过SEM、XRD、金相显微镜以及透氢动力学分析等手段考察了膜的性能,并分析了测试温度和合金组成对膜的透氢率、压力指数n值及透氢活化能的影响。前驱体（Cu/Pd/Al2O3膜）在500℃、氢气气氛中经20 h可完全合金化。在所制备的Pd–Cu合金膜中,Pd61Cu39膜的透氢性能最佳。在350~600 C,Pd45Cu55、Pd51Cu49和Pd69Cu31膜的氢通量随温度的降低而减小;Pd61Cu39和Pd63Cu37膜的氢通量随温度的降低是先减小后增大,最后又减小。随温度的降低,Pd45Cu55、Pd51Cu49和Pd69Cu31膜的渗透系数n值有增大的趋势;Pd61Cu39和Pd63Cu37膜的n值变化较为复杂。在所测温度范围,Pd45Cu55、Pd51Cu49、Pd69Cu31膜的透氢活化能分别为32.9、24.1、21.8 kJ mol 1,而Pd61Cu39和Pd63Cu37膜则不存在固定的透氢活化能。XRD测试显示：室温下Pd59Cu41、Pd61Cu39和Pd63Cu37膜的晶体结构为bcc型;Pd45Cu55、Pd51Cu49、Pd69Cu31和Pd81Cu19膜的晶体结构为fcc型。

High-loading Pt-alloy catalysts for boosted oxygen reduction reaction performance

To improve performance of membrane electrode assembly(MEA)at large current density region,efficient mass transfer at the cathode is desired,for which a feasible strategy is to lower catalyst layer thickness by constructing high loading Pt-alloy catalysts on carbon.But the high loading may induce unwanted par-ticle aggregation.In this work,H-PtNi/C with 33%(mass)Pt loading on carbon and monodisperse distri-bution of 3.55 nm PtNi nanoparticles,was prepared by a bimodal-pore route.In electrocatalytic oxygen reduction reaction(ORR),H-PtNi/C displays an activity inferior to the low Pt loading catalyst L-PtNi/C(13.3%(mass))in the half-cell.While in H_(2)-0_(2) MEA,H-PtNi/C delivers the peak power density of 1.51 W·cm^(-2) and the mass transfer limiting current density of 4.4 A·cm^(-2),being 21%and 16%higher than those of L-PtNi/C(1.25 W·cm^(-2),3.8 A·cm^(-2))respectively,which can be ascribed to enhanced mass trans-fer brought by the thinner catalyst layer in the former.In addition,the same method can be used to pre-pare PtFe alloy catalyst with a high-Pt loading of 36%(mass).This work may lead to a range of catalyst materials for the large current density applications,such as fuel cell vehicles.

Nickel boride alloys as catalysts for successive hydrogen generation from sodium borohydride solution

Nickel boride alloys,Ni-B,were prepared using chemical reduction method by the reaction of metal chloride with sodium borohydride,and heat-treated at various temperatures. The structures of the as-prepared alloys were studied using X-ray diffractometry(XRD),scanning electronic microscopy(SEM) and nitrogen adsorption-desorption analysis. When being adopted as the catalysts for successive hydrogen generation from sodium borohydride solution,the Ni-B alloy treated at 90 ℃ achieves a maximum hydrogen generation rate of 15.4 L/(min·g),and an average hydrogen generation rate of 13.6 L/min,which can give successive hydrogen supply to a 2.2 kW PEMFC at a hydrogen utilization of 100%.

Highly active and durable Pd-Cu catalysts for oxygen reduction in alkaline exchange membrane fuel cells

A Pd-Cu catalyst, with primary B2-type phase, supported by VulcanXC-7R carbon was synthesized via a solvothermal method. The catalysts were physically and electrochemically characterized by X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS）, trans- mission electron microscopy （TEM） and both cyclic and linear sweep voltammetry using a rotating disk electrode （RDE）. During the RDE testing, the half-wave potential of the Pd-Cu/Vulcan catalyst was 50 mV higher compared to that of commercial Pt/C catalyst for the oxygen reduction reaction （ORR） in alkaline media. The Pd-Cu/Vulcan exhibited a specific activity of 1.27 mA/cm2 and a mass activity of 0.59 A/mgpd at 0.9 V, which were 4 and 3 times greater than that of the commercial Pt/C catalyst, respectively. The Pd-Cu/Vulcan catalyst also showed higher in-situ alkaline exchange membrane fuel cell （AEMFC） performance, with operating power densities of 1100 MW/cm2 operating on H2/O2 and 700 MW/cm2 operating on H2/Air （CO2-free）, which were markedly higher than those of the commercial Pt/C. The Pd-Cu/ Vulcan catalyst also exhibited high stability during a short-term, in-situ AEMFC durability test, with only around 11% performance loss after 30 hours of operation, an improve- ment over most AEMFCs reported in the literature to date.

PtIr双功能催化剂膜电极制备及抗反极性能研究

燃料供应不足会导致质子交换膜燃料电池膜电极电压反转,造成阳极催化层中的碳载体发生严重腐蚀,进而给燃料电池带来不可逆的损伤。为了解决该问题,采用双功能PtIr合金作为阳极催化剂制备膜电极,并对其进行了电极极化性能、反极和交流阻抗等测试。结果表明,PtIr/C电极的峰值功率密度可达1.49 W/cm^(2),较Pt/C-IrO_(2)(50%)电极(1.46 W/cm^(2))提高2.1%。反极结果表明,PtIr/C电极抗反极时间725 s,较掺杂IrO_(2)的Pt/C电极反极性能略差,但在整个反极过程中PtIr/C电极呈现出更低的绝对反转电压,以及反极后保持更高的结构稳定性。反极后PtIr/C电极峰值功率密度降为1.18 W/cm^(2),衰减约20.80%,而Pt/C-IrO_(2)(50%)电极的峰值功率密度降至1.09 W/cm^(2),衰减约25.34%。PtIr/C电极相较掺杂IrO_(2)的Pt/C电极具有更佳的初始极化性能和优异的抗反极能力。该研究结果对质子交换膜燃料电池高性能长寿命膜电极催化层设计具有重要的意义。

Study on repairing canine mandibular defect with porous Mg-Sr alloy combined with Mg-Sr alloy membrane

To discuss the feasibility of the application of porous Mg-Sr alloy combined with Mg-Sr alloy membrane in the repair of mandibular defects in dogs.The second and third mandibular premolars on both sides were extracted from six dogs.The model of mandible buccal fenestration bone defects were prepared after the sockets healed.Twelve bone defects were randomly divided into groups A and B,then Mg-Sr alloy was implanted in bone defects of group A and covered by Mg-Sr alloy membrane while Mg-Sr alloy was implanted in bone defects of group B and covered by mineralized collagen membrane.Bone defects observed on cone beam computed tomographic images and comparing the gray value of the two groups after 4,8 and 12 weeks.After 12 weeks,the healing of bone defects were evaluated by gross observation,X-ray microscopes and histological observation of hard tissue.Bone defects in each group were repaired.At 8 and 12 weeks,the gray value of group A was higher than that of group B(P<0.05).At 12 weeks,the bone volume fraction of group A was higher than that of group B(P<0.05).The newly woven bone in group A is thick and arranged staggered,which was better than that of group B.Porous Mg-Sr alloy combined with Mg-Sr alloy membrane could further promote the repair of mandibular defects,and obtain good osteogenic effect.

氮气流量对VNbMoTaWN_(x)薄膜作为PEMFC不锈钢双极板改性层性能的影响

目的降低SS316L表面的接触电阻,提高耐腐蚀性能。方法采用非平衡场磁控溅射离子镀技术在SS316L不锈钢表面制备VNbMoTaW和不同氮气流量的VNbMoTaWN_(x)薄膜。使用场发射扫描电镜、XRD衍射仪、XPS光电子能谱仪、电化学工作站、接触电阻测试装置,研究了改性涂层的组成和结构对接触电阻和耐腐蚀性能的影响。结果扫描电子显微镜结果表明,所有薄膜表面致密且连续、与基体结合良好。随着氮气流量的增加,氮化物相逐渐增多、柱状晶结构减少、薄膜更加致密紧凑。XRD结果表明,未通氮气的高熵合金薄膜具有高熵合金体心立方结构,并沿(110)晶面方向生长。随着氮气流量的增加,氮化物相逐渐增多,薄膜晶体结构开始从体心立方结构转变为面心立方结构。结合XPS分析结果可知,VNbMoTaWN_(x)薄膜表面主要由金属氮化物和少量高熵合金BCC相组成,并且随着氮气流量的增加,金属氮化物相逐渐增多。与单层VNbMoTaW薄膜相比,VNbMoTaWN_(x)薄膜具有更好的耐腐蚀性和导电性能。氮流量为12mL/min的高熵合金氮化物薄膜具有最优异的综合性能。表面改性后的薄膜接触电阻大幅度降低,在1.4MPa的压力下,与碳纸的接触电阻仅为12.2 mΩ·cm^(2),接近美国能源部(DOE)的技术目标。由动电位极化曲线测得VNbMoTaWN_(x)-12mL/min在模拟PEMFC阴极环境下的腐蚀电流密度为0.040μA/cm^(2),与SS316L基体相比,薄膜的耐腐蚀性得到了很大提升。在0.6 V恒电位模拟阴极环境下,VNbMoTaWN_(x)-12 mL/min的电流密度稳定在1.01μA/cm^(2),接近美国能源部1μA/cm^(2)的目标。结论VNbMoTaW和不同氮气流量的VNbMoTaWN_(x)薄膜能显著提高SS316L基体的耐腐蚀性和导电性能。

ETFE膜在怀柔科学城城市客厅A地块项目中的应用

ETFE膜因其良好的透视和遮阳功能,能够有效避免阳光照射进玻璃幕墙而导致的室内温度过高,但其施工经验尚有不足。研究结合怀柔科学城城市客厅A地块项目,充分考虑了施工技术和施工组织管理的重难点,详细介绍了ETFE膜的施工全过程,保证了施工质量,丰富了施工经验。

Preparation and Characterization of Ultra-thin Pd-Ag Alloy Membranes

Ultra-thin Pd-Ag alloy membranes were prepared initially by cold rolling, and it was found that there exist a large number of defects such as pinholes or cracks in the as-rolled membranes. Subsequently, these defects were repaired using electroless plating technique. The morphologies of the membranes have been examined by scanning electron microscopy （SEM）. It was observed in some as-repaired membranes that the defects were disappeared. A hydrogen permeation study has demonstrated that the as-repaired Pd-Ag alloy membranes were of high hydrogen permeation flux and hydrogen selectivity.

Electrocatalytic reduction of nitrate using Pd-Cu modified carbon nanotube membranes

Excessive nitrate in water is harmful to the ecological environment and human health.Electrocatalytic reduction is a promising technology for nitrate removal.Herein,a Pd-Cu modified carbon nanotube membrane was fabricated with an electrodeposition method and used to reduce nitrate in a flowthrough electrochemical reactor.The optimal potential and duration for codeposition of Pd and Cu were-0.7 V and 5 min,respectively,according to linear scan voltammetry results.The membrane obtained with a Pd:Cu ratio of 1:1 exhibited a relatively high nitrate removal efficiency and N_(2)selectivity.Nitrate was almost completely reduced(~99%)by the membrane at potentials lower than-1.2 V.However,-0.8 V was the optimal potential for nitrate reduction in terms of both nitrate removal efficiency and product selectivity.The nitrate removal efficiency was 56.2%,and the N_(2)selectivity was 23.8%for the Pd:Cu=1:1 membrane operated at-0.8 V.Nitrate removal was enhanced under acidic conditions,while N_(2)selectivity was decreased.The concentrations of Cl-ions and dissolved oxygen showed little effect on nitrate reduction.The mass transfer rate constant was greatly improved by 6.6 times from 1.14×10^(-3)m/h at a membrane flux of 1 L/(m^(2)·h)to 8.71×10^(-3)m/h at a membrane flux of 15 L/(m^(2)·h),which resulted in a significant increase in the nitrate removal rate from 13.6 to 133.5 mg/(m^(2)·h).These findings show that the Pd-Cu modified CNT membrane is an efficient material for nitrate reduction.

PEMFC铝合金双极板表面改性研究现状与发展

质子交换膜燃料电池(Proton Exchange Membrane Fuel Cell,PEMFC)作为第五代燃料电池,是最具发展前景的新能源电池,其中双极板作为PEMFC的核心元件,不仅能将单一电池链接起来形成电池堆,起到支撑作用,还具有提供气体流道、隔绝阴阳极两端等作用,对燃料电池工作性能、寿命起到关键作用。其中铝合金作为一种具有良好导电性能、成本低、轻质的材料,在PEMFC双极板材料方面应用潜力巨大。但铝合金双极板耐腐性不佳,在PEMFC工作环境下极易被腐蚀,且其表面生成的钝化膜,增大了电池的接触电阻,从而对电池性能和寿命产生不利影响,而通过铝合金表面改性是解决该问题的主流方法。首先概述了PEMFC原理、双极板材料类型及内部环境,然后阐述了PEMFC中铝合金双极板的服役问题,并对近年来铝合金双极板的表面改性进行分类。重点概括了铝合金表面金属及其化合物涂层(贵金属、金属氮/碳化物、镍磷金属涂层)与非金属涂层(碳基涂层、高分子聚合物涂层)的结构设计、成分优化、服役性能特点。分析结果表明,选用低成本、具有良好耐蚀性和导电性的金属惨杂的无定型碳、金属碳/氮化物涂层,能降低双极板生产成本,提高双极板工作性能,并对涂层设计出多层复合涂层,能打断涂层中的细长针孔缺陷,提高涂层的完整性和致密性。在铝合金表面进行改性研究,以提高其耐蚀性、导电性及服役稳定性,对推动铝合金双极板在PEMFC电堆中的应用至关重要。