光催化沉积法制备Pd膜的改进及Pd膜性能表征

对光催化沉积法(PCD)制备Pd膜进行了改进,使含有TiO2与Pd2 的悬浮液膜层在多孔陶瓷膜表面形成液体薄膜,该薄膜在紫外光直接照射下发生光催化还原反应,烧结后得到含TiO2及Pd晶种的超薄膜层,用化学镀修饰得致密Pd膜.采用SEM、EDAX方法对所制的Pd膜表征结果表明,Pd膜厚度为5~6μm.在350~500℃和0.05~0.15 MPa下进行气体渗透实验,当温度为450℃时,H2渗透系数为4.07×10-6mol/(m2.s.Pa),N2的渗透量检测不出,高温热循环测试表明该Pd膜致密且具有良好的热稳性.     

Pd/TiAl膜的制备研究

采用无电镀技术在多孔TiAl金属问化合物支撑体上制备了Pd膜.用SEM测定Pd膜的表面和断面的形貌,EDS测定从膜层到支撑层元素的组成,结果表明,支撑体表面形成了均匀致密的Pd膜,膜层的主要成分是单质Pd,所制钯膜的厚度为2～3μm.在350℃～500℃的温度范围内考察Pd膜透氢性能,当500℃,0.1 MPa时,H2的渗透系数为4.0×10-6mol·m-2·s-1·Pa-1,H2/N2的分离系数为30.测得本文所制备Pd膜的活化能为10.8 kJ/mol.     

废催化剂中Pd的回收及循环利用

在六苄基六氮杂异伍兹烷(HBIW)的催化氢解反应中，所用催化剂是Pd(OH)2／C，而Pd属于贵金属，它的回收利用直接影响着最终产品的成本核算。对HB研的催化氢解反应中产生的废催化剂进行了回收，并将回收所得金属钯重新制备成催化剂。再次用于HBIW的催化氢解反应，其活性与以PdCl2为前体制备的催化剂活性相当。回收的金属钯纯度为99．6％，回收率为92％-94％。     

Pd/WS2二维复合材料的制备及电解水制氢性能研究

首先通过锂离子插层制备了薄层WS_2纳米片,并采用软模板法在纳米片上负载了Pd纳米颗粒,得到Pd/WS_2复合材料。X射线衍射光谱(XRD)和透射电子显微镜(TEM)的结果表明Pd颗粒均匀地负载在了WS_2纳米片上。随后在H_2SO_4水溶液中对该复合材料进行电解水析氢性能测试,线性扫描伏安法(LSV)结果表明:复合材料的析氢起始电位为155 mV,塔菲尔斜率为121.79 mV·dec~(-1),总体催化性能相比于单纯的WS_2纳米片和Pd金属颗粒有很大的改善,也优于当前商用的Pd/C催化剂。采用循环伏安法(CV)测试其稳定性,结果表明Pd/WS_2复合物电极具有优良的电催化析氢稳定性。     

表面钯–磷膜对LaNi_(4.25)Al_(0.75)材料贮氢性能的影响

以机械粉化的La Ni4.25Al0.75贮氢合金粉末为基底材料,对其表面进行Pd–P化学镀覆。通过扫描电镜、能谱仪、X射线衍射仪等对沉积膜层的表面形貌和成分结构进行表征和分析。考察了化学镀覆Pd–P前后La Ni4.25Al0.75合金粉末的贮氢性能。结果表明,在La Ni4.25Al0.75颗粒表面化学镀覆Pd–P膜层能够改善其抵抗O2和N2毒化作用的能力。     

TiCl_3/PdCl_2法活化多孔陶瓷基体制备透氢Pd膜

以TiCl3取代SnCl2作为敏化剂,考察TiCl3/PdCl2活化法对Pd膜制备及性能的影响。所制备Pd膜的表面与断面形貌采用SEM与金相显微镜表征,测试膜的透氢性、选择性以及高温稳定性,比较了TiCl3/PdCl2与SnCl2/PdCl22种活化方法对Pd沉积速率的影响。结果表明:TiCl3/PdCl2活化法同样能够在多孔陶瓷基体表面形成活性催化层,并最终成功获得高性能的Pd膜。相对而言,TiCl3/PdCl2活化法更有利于Pd膜的快速形成,而且彻底避免了Sn对Pd膜的污染,有望成为SnCl2/PdCl2活化法的一种理想替代方法。     

化学镀—电镀结合法制备的Pd-Cu/Al2O3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。     

超薄Pd～Cu／Al2O3合金膜的透氢性能

以多孔Al2O3陶瓷管为基体,采用化学镀法分步沉积Pd和Cu金属层,再经高温合金化处理,制备组分不同的Pd-Cu合金膜,膜厚均约为4μm.研究合金膜在100~650℃范围内的透氢性能,考察温度和膜组成对透氢性能的影响.结果表明:H2在膜表面的扩散过程是H2渗透速率的主要控制步骤;温度对膜透氢性能的影响规律因膜组成而异,这可能与合金膜在不同组成、不同温度条件下所呈现的晶相结构有关.     

高分散Pd/Ni-A-CA纳米催化剂催化喹啉加氢

以镍(Ni)为金属节点，腺嘌呤(A)和柠檬酸(CA)为有机配体，采用溶剂热法制备了非晶态金属有机配合物Ni-A-CA。将Pd Cl₂溶液浸渍于载体Ni-A-CA后用NaBH₄还原制得高分散的Pd纳米粒子(Pd NPs)催化剂Pd/Ni-A-CA。通过SEM、TEM、XRD、FTIR、XPS、N₂吸附-脱附对载体Ni-A-CA[n(Ni)∶n(A)∶n(CA)=2∶1∶1.5]和催化剂3%Pd/Ni-A-CA(3%为Pd的理论负载量，以Ni-A-CA的质量计，下同)进行了表征。结果表明，Pd NPs高度分散在载体Ni-A-CA上，其粒径为(2.2±0.3) nm，且载体与Pd NPs之间存在的强相互作用增强了催化剂的催化性能。在90℃、2 MPa H₂条件下，3%Pd/Ni-A-CA催化喹啉加氢反应70 min，喹啉转化率为99.0%，生成1,2,3,4-四氢喹啉选择性>99%。     

纳米晶Pd修饰p-Si电极的制备及其光电析氢性能

在半导体p型Si上化学沉积金属Pd,制备了纳米晶Pd修饰p-Si电极.控制化学沉积的时间,可得到不同沉积量和不同尺度的Pd颗粒,沉积时间为20 min时,Pd颗粒的直径约为80 nm.XRD测试结果表明,Pd颗粒的平均晶粒尺寸为7.37 nm.重点研究了Pd/p-Si电极在光照前后的催化析氢性能.光照下Pd/p-Si电极的析氢过电位较无光照减小约250 mV,比半导体Si减小约450 mV（电流密度为2.5 mA•cm^-2时）.电化学交流阻抗谱（EIS）表明,光照下Pd/p-Si电极的电化学析氢反应电阻由未光照的593.12 Ω•cm2降低至442.20Ω•cm²,光照下的析氢反应速率明显增加.     

钯膜制备新技术

介绍了钯膜的制备方法及在载体上制备越薄钯膜的改进技术，由无电子电镀过程制备的钯膜对氢渗透速率高，对氢有良好的选择性，由金属有机气相沉积法（MOCVD）在载体孔内沉积钯膜有助于防止氢的脆化作用，利用渗透压的新技术可控制膜的微观结构和孔隙率。将多孔不锈钢作为载体时，利用不同的技术能克服氢的脆化作用，减少钯膜厚度以及防止钯－银层与不锈钢间金属原子的相互扩散，由光催化沉积可在半导体载体上制备越薄钯膜。     

Effects of Sn residue on the high temperature stability of the H_2-permeable palladium membranes prepared by electroless plating on Al_2O_3 substrate after SnCl_2–PdCl_2 process: A case study

The stability of composite palladium membranes is of key importance for their application in hydrogen energy systems. Most of these membranes are prepared by electroless plating, and beforehand the substrate surface is activated by a SnCl_2–PdCl_2 process, but this process leads to a residue of Sn, which has been reported to be harmful to the membrane stability. In this work, the Pd/Al_2O_3 membranes were prepared by electroless plating after the SnCl_2–PdCl_2 process. The amount of Sn residue was adjusted by the SnCl_2 concentration, activation times and additional Sn(OH)_2coating. The surface morphology, cross-sectional structure and elemental composition were analyzed by scanning electron microscopy(SEM), metallography and energy dispersive spectroscopy(EDS), respectively. Hydrogen permeation stability of the prepared palladium membranes were tested at450–600 °C for 400 h. It was found that the higher SnCl_2 concentration and activation times enlarged the Sn residue amount and led to a lower initial selectivity but a better membrane stability. Moreover, the additional Sn(OH)_2coating on the Al_2O_3 substrate surface also greatly improved the membrane selectivity and stability.Therefore, it can be concluded that the Sn residue from the SnCl_2–PdCl_2 process cannot be a main factor for the stability of the composite palladium membranes at high temperatures.     

Development of thin palladium membranes supported on large porous 310L tubes for a steam reformer operated with gas-to-liquid fuel

Palladium membranes were prepared on large tubes (80 mm diameter and 150 mm length) of porous stainless steel supports (PSS) using a modified electroless plating technique. The morphology of the palladium layer was found to be depending on the container material of the coating apparatus. The use of PMMA resulted in compact palladium layers with smooth surfaces whereas PTFE led to inhomogeneous palladium coating with rough surface. Two different ceramic materials and coating methods were used to prepare an intermediate layer needed to prevent intermetallic diffusion between the palladium and the support at elevated temperatures. Wet powder spraying of TiO₂ followed by sintering resulted in a smoother surface than atmospheric plasma spraying of YSZ, thus allowing for a thinner palladium coating. Pd/TiO₂/PSS membranes showed about 4 times higher hydrogen permeances than Pd/YSZ/PSS membranes as a consequence of higher palladium thickness and lower porosity of the ceramic intermediate layer. The selectivity against nitrogen was comparable for both membranes. However, the YSZ intermediate layer showed better stability at elevated temperatures. Two membrane tubes were applied in the membrane reformer, which produced hydrogen successfully from a gas-to-liquid (GtL) fuel.     

Surface modification of macroporous Al2O3 tubes with carbon-doped TiO2 intermediate layer and preparation of highly permeable palladium composite membranes for hydrogen separation

ABSTRACT

To prepare H₂-permeable palladium composite membranes, a novel carbon-doped microporous TiO₂ intermediate layer was introduced to modify the surface of macroporous Al₂O₃ substrates. The Pd/TiO₂–C/Al₂O₃ membrane was prepared via electroless plating, and thereafter, carbon residue in the intermediate layer was removed by calcination in air, yielding a Pd/TiO₂/Al₂O₃ membrane. Experimental results indicate that the carbon residue shrinks the pore size of the intermediate layer and facilitates a decrease of membrane defects. Additionally, carbon removal induces a higher effective membrane area at the permeate side, which enhances hydrogen permeability. Furthermore, the apparent activation energy (E_A) and stability of the as-prepared Pd/TiO₂/Al₂O₃ membrane were investigated.     

Experimental demonstration of enhanced hydrogen permeation in palladium via a composite catalytic‐permselective membrane

A composite catalytic‐permselective (CCP) membrane comprised of a 500‐μm Cu(II)O/Al₂O₃ catalyst film washcoated overtop a 27‐μm electroless‐plated dense palladium thin film was constructed on a porous less‐steel substrate. Hydrogen purification experiments performed under ideal (H₂–Ar) nonreactive mixtures and simulated reformate (5% CO, 7.5% H₂O, 15% H₂, 1.5% CO₂, and balance Ar) over a range of residence times at 623–773 K confirm up to 30% enhancement in observed hydrogen permeance of the palladium film, achieved using the CCP membrane design in which the catalyst layer modifies the gas‐phase composition in direct contact with the permselective Pd film. Scanning electron microscopy analysis of the palladium film after ～10‐h exposure to reaction conditions and Cu(II)O catalyst confirm no corrosion of the film, while observed hydrogen permselectivities remained in excess of 10,000:1. These experimental results confirm that the CCP membrane design is capable of significantly improving palladium membrane performance. © 2012 American Institute of Chemical Engineers AIChE J, 59: 1627–1634, 2013     

Application of electroless procedures to the preparation of palladium catalysts

The influence of various (laser, UV lamp and thermal) activation treatments on the diffuse reflectance and ESR spectra of CeO₂ are examined. Ceria-supported palladium catalysts are prepared by electroless deposition of the metal from palladium chloride and hydrazine hydrate solutions. The atomic defects induced in ceria by the activation procedures appear to initiate the palladium deposition.On leave from the General Physics Institute of the Russian Academy of Sciences.     

Fabrication of Palladium Membranes Supported on a Silicalite‐1 Zeolite‐Modified Alumina Tube for Hydrogen Separation

Thin palladium membranes were fabricated on macroporous α‐Al₂O₃ tubes by electroless plating. The silicalite‐1 (Sil‐1) zeolite serving as intermediate and diffusion barrier layer was introduced to modify the surface roughness and pore size of the porous substrate and prevent the atomic interdiffusions of the metal elements between Pd layer and the support. The Pd composite membranes were studied by scanning electron microscopy (SEM), X‐ray diffraction (XRD), and electron probe microanalysis (EPMA), revealing that morphology and structure of the Sil‐1 layer significantly influence the Pd membrane preparation. Single‐gas permeation tests were carried out with gas H₂ and N₂ to determine the permeation performance of the membranes. The resulting membrane exhibited long‐term stability under hydrogen permeation.     

An integrated purification and production of hydrogen with a palladium membrane-catalytic reactor

In this paper, we presented an integrated production and purification process of hydrogen by the use of a defect-free palladium membrane. Hydrogen could be purified from a variety of mixtures providing the purity of 3–7 N depending on the feeding stream. The permeation parameters are accurately predicted by a separation model as established. The membrane is prepared by electroless plating and is stable among 300–400°C. Using an active catalyst, the rate of steam reforming of methanol was found to be significantly faster than that without a membrane module. In the steam reforming of methane, the reaction temperature was lowered to 500°C to achieve a conversion of 45%, which is 15% higher than the thermodynamic equilibrium conversion.     

Direct production of hydrogen peroxide from oxygen and hydrogen applying membrane-permeation mechanism

Direct synthesis of hydrogen peroxide is conducted using a palladium membrane reactor. The palladium membrane is prepared on the external surface of the porous α-alumina tubing, by electroless plating (ELP) or chemical vapor deposition (CVD). Thus prepared membrane is immersed into aqueous reaction solution. Hydrogen is supplied from inside of the palladium membrane, while oxygen was bubbled in the reaction solution. Both reacted at the surface of the membrane to produce hydrogen peroxide. Hydrogen peroxide is produced steadily for more than 80 h and the selectivity based on the amount of reacted hydrogen was estimated to be ca. 50%. The reactor performance is investigated in correlation with membrane properties and the hydrogen/oxygen supply pressures.     

Facile surface modification of porous stainless steel substrate with TiO2 intermediate layer for fabrication of H2-permeable composite palladium membranes

The increasing demand in compact hydrogen separators greatly stimulated the investigation and utilization of composite palladium membranes. Porous stainless steel (PSS) tubes were chosen as substrate material in this study, and a novel process of carbon-assisted solid-state sintering was introduced to modify the PSS surface with a TiO₂ layer. A Pd/TiO₂/PSS membrane with a Pd thickness of 6 µm was successfully fabricated via electroless plating. Scanning electron microscopy (SEM), metallographic microscopy, X-ray diffraction and pore-size analyses were performed for material characterizations. As measured by H₂/N₂ single-gas testing, the fabricated Pd/TiO₂/PSS membrane is permeable and selective to hydrogen, and it was stable during a time-on-stream of 100 h under 450°C.