合金成分对Ag-Cu二元合金制备纳米多孔银的影响

本文研究了纳米多孔银的制备及合金成分对纳米多孔银微观结构的影响。选用Ag含量(原子百分数)为15%,20%和25%(分别对应亚共晶,共晶与过共晶成分)的Ag-Cu合金薄带,通过化学去合金法制得具有三维的,韧带-孔洞双连续结构的纳米多孔银。利用X射线衍射仪(XRD)与扫描电子显微镜(SEM)对试样进行物相组成和微观结构的观察与分析。研究了Cu含量的变化对纳米多孔银微观结构及性能的影响。得出结论:去合金介质及温度等腐蚀条件一定的情况下,去合金时间越长,纳米多孔银的韧带尺寸越大。在腐蚀介质和温度等条件相同的情况下,纳米多孔结构特征尺寸受合金成分影响,Cu含量越高,去合金过程中产生的孔洞/通道尺寸越大。由于Cu含量不同,Ag15Cu85,Ag20Cu80和Ag25Cu80三种成分的合金中,Ag20Cu80去合金化得到的纳米多孔Ag的韧带孔洞微观结构最均匀。     

Cu-Au-Ag三元去合金化制备纳米多孔金材料

采用磁控溅射镀铜金银多层膜,经过长时间高温热处理合金化制备前驱体三元合金,以不同的酸溶液自由腐蚀去合金化去除合金中的铜元素和银元素,成功制备出纳米多孔金薄膜。采用扫描电镜和X射线能谱仪对去合金腐蚀前后样品的形貌和成分进行了分析。结果表明,400℃,36h热处理后铜金银多层膜完全合金化,获得了Au_3Ag_(28.5)Cu_(68.5)合金材料;FeCl_3+HCl溶液自由腐蚀去除铜可获得连续均匀的纳米尺寸孔隙结构,获得了几乎不含铜的样品;采用渐进浓度的硝酸自由腐蚀去合金化后去除银后获得了孔隙率约84%的纳米多孔金薄膜,其微观结构为连续的三维多孔结构,其系带尺寸10~35nm,并且20~25nm的系带分布达77%。     

Pd-Ag合金纳米粒子合成及其催化性能研究

采用W/O微乳液法合成Pd-Ag合金纳米粒子并结合微乳浸渍工艺制备了负载型Pd-Ag/Al_2O_3催化剂。利用紫外-可见分光光度计和透射电子显微镜对合成的Pd-Ag合金纳米粒子进行表征,并考察了对乙炔加氢反应的催化性能。结果表明,在聚氧乙烯(4)月桂醚(Brij30)/正辛烷/水微乳液体系中加入聚乙烯基吡咯烷酮(PVP),对生成的纳米粒子起到二次保护作用,Pd与Ag以合金纳米粒子形式稳定存在且粒径大小均一,粒径在1～2nm,可随PVP以薄膜形态负载并分散在Al_2O_3表面。当PVP相对分子质量为8000～10000,cPVP8:c(Pd+Ag)=0.1时,合成的Pd-Ag合金纳米粒子数量最多,粒径最小,制备的Pd-Ag/Al_2O_3催化剂具有良好的乙炔加氢活性和选择性。     

Ag15Cu85二元合金高温氧化行为对去合金机制的影响

近年来,纳米多孔材料成为光催化、储能等领域的研究热点.本工作将高温氧化和去合金工艺相结合,研究高温氧化对Ag15 Cu85二元合金前驱体制备纳米多孔银的影响.在650～750℃温度下,氧化1～5 min,Ag15 Cu85二元合金表面产生纳米级二维微孔、颗粒析出物及岛状平台.随着氧化时间的延长,合金表面呈现出相似的微观氧化形貌.铸态合金薄带在60℃、5％HNO3(质量分数)中去合金0.5 h时,合金表面活性组元溶解;去合金进行1.5 h时,获得三维双连续的纳米多孔银结构.氧化态前驱体在腐蚀溶液浓度相同、去合金温度更低(45℃)的情况下,去合金15 min就能得到均匀的韧带和孔隙尺寸更大的纳米多孔银,仅为铸态合金薄带去合金持续时间的1/6.这说明氧化行为对去合金过程产生了较大影响,高温氧化改变了去合金反应的中间过程,去合金反应的参与者由单一α?Cu(Ag)固溶体转变为α?Cu(Ag)固溶体和Cu的氧化产物.氧化产物参与去合金反应,极大地促进了去合金反应进程,提高了活性组元溶解效率.     

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0.2μm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773 K ,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5μm)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.     

甲醇燃料电池纳米催化剂研制成功

厦门大学化学化工学院以XC-72R炭黑为载体,制备出直接甲醇燃料电池阳极PtRu/C纳米催化剂——纳米PtRu/C合金催化剂,其活性与目前商业     

钯催化剂在燃料电池阳极中的研究进展

钯(Pd)作为燃料电池阳极催化剂,具有重要的市场应用前景。从纯Pd催化剂,负载型Pd催化剂,Pd基合金催化剂3个方面综述了近年来Pd催化剂在燃料电池阳极中的研究进展,介绍了其结构形态、载体、掺杂元素等对Pd催化剂的催化性能的影响。     

脱合金化法制备纳米多孔铂合金的研究进展

纳米多孔金属由纳米尺度的孔隙和金属韧带组成，具有三维双连通的网络状结构，兼具纳米材料和金属材料的双重特性，在催化、传感和药物输送等领域具有广阔的应用前景。脱合金化法操作简单，工艺流程短，成本相对较低，是制备纳米多孔金属的常用方法。目前，利用脱合金化法制备的纳米多孔Pt合金因其对甲醇氧化和氧还原反应具有优异的催化活性而备受关注，有望在燃料电池等相关领域实现应用。近年，研究学者不断丰富纳米多孔Pt合金的合金体系，通过优化合金成分和脱合金化工艺对其结构和性能进行调控，发展出多种形态的纳米多孔Pt合金，系统调查了前驱体的结构和成分、脱合金工艺参数对纳米多孔Pt合金的组织结构、形貌和性能的影响，并对纳米多孔形成和优异性能的机理进行了广泛的研究。利用脱合金化法制备的纳米多孔Pt合金具有多种形态，如低维的纳米颗粒、纳米花、纳米线和薄膜以及三维的纳米多孔带材等。低维的纳米多孔Pt合金因其更大的比表面积和纳米尺寸效应而具有更为突出的催化活性，而三维的纳米多孔带材具有均匀的纳米多孔结构，且克服了低维合金易团聚的问题。通过调整前驱体合金的化学成分和组织结构，改变脱合金化工艺参数，以及对纳米多孔合金进行退火处...     

Cu对Pd/C电催化乙醇氧化性能的影响

以活性碳(Vulcan XC-72)为载体,用改良的化学还原法制备不同Pd:Cu比例的Pd_x-Cu/C催化剂,使用X-射线衍射(XRD)、透射电镜(TEM)、X-射线光电子能谱(XPS)和电化学方法对其进行了表征,研究了Cu对Pd/C催化剂催化性能的影响。结果表明:随着Pd与Cu原子比的提高Pd_x-Cu/C催化剂的催化活性先提高后降低,当Pd:Cu=8:1时Pd8-Cu/C催化剂粒子均匀分散在碳载体表面,其直径约为2.8 nm;在催化剂中掺入的少量Cu元素部分进入Pd晶格形成了合金。这种催化剂在混合水溶液中表现出最佳的催化活性和稳定性,对C_2H_5OH氧化的催化峰电流密度达到114 m A/cm~2,是Pd/C的2.5倍,是JM-Pd/C的3.6倍。     

纳米晶Cu-Al合金去合金化制备纳米多孔铜及其力学性能研究

采用高能球磨结合放电等离子烧结技术(SPS)制备了纳米晶Cu-Al合金,进而通过去合金化法获得纳米多孔铜块体材料。研究了合金成分对纳米晶Cu-Al前驱体物相演变、去合金化处理获得的纳米多孔铜微观结构和力学性能的影响。结果表明,当合金中铜含量较低时,纳米晶Cu-Al前驱体由α-Al固溶体和Al_2Cu两相组成;随着铜含量的增加,前驱体中α-Al固溶体相逐渐减少,Al_2Cu相逐渐增加;当铜含量增加到32%时,纳米晶Cu-Al前驱体中仅有Al_2Cu单相。此外,随着铜含量的增加,纳米晶Cu-Al前驱体去合金化处理后,其纳米多孔铜微观结构由微米/纳米双级复合孔逐渐转变为孔径均匀的三维连通纳米孔,并且纳米多孔铜块材的压缩强度逐渐增大。     

Structure and properties of nanoporous FePt fabricated by dealloying a melt-spun Fe_(60)Pt_(20)B_(20) alloy and subsequent annealing

A nanoporous FePt alloy has been fabricated by dealloying a melt-spun Fe(60)Pt(20)B(20)alloy composed of nanoscale amorphous and face-centered-cubic FePt(fcc-FePt)phases in H2 SO4 aqueous solution.The nanoporous alloy consists of single fcc-FePt phase with an Fe/Pt atomic ratio of about 55.3/44.7,and possesses a uniform interpenetrating ligament-channel structure with average ligament and pore sizes of 27 nm and 12 nm,respectively.The nanoporous fcc-FePt alloy shows soft magnetic characteristics with a saturation magnetization of 37.9 emu/g and better electrocatalytic activity for methanol oxidation than commercial Pt/C in acidic environment.The phase transformation from disordered fcc-Fe Pt into ordered face-centered-tetragonal FePt(L10-FePt)in the nanoporous alloy has been realized after annealing at823-943 K for 600 s.The volume fraction of the L10-FePt phase in the alloy increases with the rise of annealing temperature,which results in the enhancements of coercivity and saturation magnetization from 0.14 kOe and 38.5 emu/g to 8.42 kOe and 51.4 emu/g,respectively.The ligament size of the samples is increased after annealing.     

Facile ultrafine copper seed-mediated approach for fabricating quasi-two-dimensional palladium-copper bimetallic trigonal hierarchical nanoframes

Anisotropic Pd nanoparticles with highly branched morphologies are urgently needed as building blocks for nanoscale devices,catalysts,and sensing materials owing to their novel structures and unique physicochemical properties.However,realizing size control and branch manipulation for these materials is very challenging.In this study,we develop a facile ultrafine Cu seed-mediated approach in the aqueous phase to produce novel Pd-Cu trigonal hierarchical nanoframes (THNFs).The main branch of most of the obtained nanocrystals is tripod-like,with advanced branches along the arms as frame units having self-similarity.In this method,the size of the Pd-Cu THNFs can be flexibly controlled by manipulating the nucleation involving the sub-3 nm Cu seeds.These Pd-Cu THNFs outperform Pd black with regard to their ethanol-oxidation performance,having a specific activity and mass activity 9.7 and 6.6 times higher,respectively.This research provides a versatile ultrafine seed-mediated approach for producing size-controlled anisotropic bimetallic nanoframes.     

High Strength and Ductile Bulk Quasi‐crystalline Alloys

Quinary Zr‐Al‐Ni‐Cu‐(Ag or Pd) amorphous alloys exhibit a double‐stage devitrification on heating. Primary devitrification leads to the precipitation of nanoscale icosahedral particles with a size from 20 to 50 nm. High nucleation and low growth rates are obtained in a polymorphous mode for the Ag‐containing alloys and a diffusion‐controlled mode for the Pd‐containing alloys. The nanoscale mixed structure alloys exhibit improved strength and ductility as compared to the corresponding amorphous single‐phase alloys.     

Hierarchical Nanoporous Copper Architectures via 3D Printing Technique for Highly Efficient Catalysts

Nanoporous metals represent a class of functional materials with unique bicontinuous open porous structural properties, making them ideal candidates for various catalyst applications. However, the pursuit of nanoporous properties, extremely small pores, and high surface area, results in the restriction of mass transport. Herein, a free‐standing hierarchical nanoporous Cu material, prepared by a selective laser melting 3D printing technique and a one‐step dealloying process, is presented as a highly efficient electrocatalyst for methanol oxidation. It is demonstrated that the digitally controlled hierarchical structure with macro‐ and nano‐scaled pores can be utilized for promoting and directing mass transport as well as for the enhancement of catalytic properties. This work highlights a facile, low‐cost, and alternative strategy for hierarchical nanoporous structure design that can be applied to binary, ternary, and quaternary metal alloys for various functional applications.     

Nanoporous Gold Bowls: A Kinetic Approach to Control Open Shell Structures and Size‐Tunable Lattice Strain for Electrocatalytic Applications

Controlling sub‐10 nm ligament sizes and open‐shell structure in nanoporous gold (NPG) to achieve strained lattice is critical in enhancing catalytic activity, but it remains a challenge due to poor control of reaction kinetics in conventional dealloying approach. Herein, a ligament size‐controlled synthesis of open‐shell NPG bowls (NPGB) through hetero‐epitaxial growth of NPGB on AgCl is reported. The ligament size in NPGB is controlled from 6 to 46 nm by varying the hydroquinone to HAuCl₄ ratio. The Williamson–Hall analysis demonstrates a higher lattice strain in smaller ligament size. In particular, NPGB with 6 nm (NPGB 6) ligament size possess the highest strain of 15.4 × 10^?3, which is nearly twice of conventional 2D NPG sheets (≈8.8 × 10^?3). The presence of high surface energy facets in NPGBs is also envisaged. The best electrocatalytic activity toward methanol oxidation is observed in NPGB 6 (27.8 μA μg^?1), which is ≈9‐fold and 3‐fold higher than 8 nm solid Au nanoparticles, and conventional NPG sheets. The excellent catalytic activity in NPGB 6 is attributed to the open‐shell structure, lattice strain, and higher electro‐active surface area, allowing efficient exposure of catalytic active sites to facilitate the methanol oxidation. The results offer a potential strategy for designing next generation electrocatalysts.     

Chemical Design of Palladium‐Based Nanoarchitectures for Catalytic Applications

Palladium (Pd) plays an important role in numerous catalytic reactions, such as methanol and ethanol oxidation, oxygen reduction, hydrogenation, coupling reactions, and carbon monoxide oxidation. Creating Pd‐based nanoarchitectures with increased active surface sites, higher density of low‐coordinated atoms, and maximized surface coverage for the reactants is important. To address the limitations of pure Pd, various Pd‐based nanoarchitectures, including alloys, intermetallics, and supported Pd nanomaterials, have been fabricated by combining Pd with other elements with similar or higher catalytic activity for many catalytic reactions. Herein, recent advances in the preparation of Pd‐based nanoarchitectures through solution‐phase chemical reduction and electrochemical deposition methods are summarized. Finally, the trend and future outlook in the development of Pd nanocatalysts toward practical catalytic applications are discussed.     

Recent progress in the structure control of Pd–Ru bimetallic nanomaterials

Pd and Ru are two key elements of the platinum-group metals that are invaluable to areas such as catalysis and energy storage/transfer. To maximize the potential of the Pd and Ru elements, significant effort has been devoted to synthesizing Pd–Ru bimetallic materials. However, most of the reports dealing with this subject describe phase-separated structures such as near-surface alloys and physical mixtures of monometallic nanoparticles (NPs). Pd–Ru alloys with homogenous structure and arbitrary metallic ratio are highly desired for basic scientific research and commercial material design. In the past several years, with the development of nanoscience, Pd–Ru bimetallic alloys with different architectures including heterostructure, core-shell structure and solid-solution alloy were successfully synthesized. In particular, we have now reached the stage of being able to obtain Pd–Ru solid-solution alloy NPs over the whole composition range. These Pd–Ru bimetallic alloys are better catalysts than their parent metal NPs in many catalytic reactions, because the electronic structures of Pd and Ru are modified by alloying. In this review, we describe the recent development in the structure control of Pd–Ru bimetallic nanomaterials. Aiming for a better understanding of the synthesis strategies, some fundamental details including fabrication methods and formation mechanisms are discussed. We stress that the modification of electronic structure, originating from different nanoscale geometry and chemical composition, profoundly affects material properties. Finally, we discuss open issues in this field.     

Electrochemical Fabrication of Pd-Ag Alloy Nanowire Arrays in Anodic Alumina Oxide Template

The synthesis of Pd-Ag alloy nanowires in nanopores of porous anodic aluminum oxide （AAO） template by electrochemical deposition technique was reported. Pd-Ag alloy nanowires with 16%-25% Ag content are expected to serve as candidates of useful nanomaterials for the hydrogen sensors. Scanning electron microscopy （SEM） and energy dispersed X-ray spectroscopy （EDX） were employed to characterize the morphologies and compositions of the Pd-Ag nanowires. X-ray diffraction （XRD） was used to characterize the phase properties of the Pd-Ag nanowires. Pd-Ag alloy nanowire arrays with 17.28%-23.76% Ag content have been successfully fabricated by applying potentials ranging from -0.8 to -1.0 V （vs SCE）. The sizes of the alloy nanowires are in agreement with the diameter of AAO nanopores. The underpotential deposition of Ag＋ on Pd and Au plays an important role in producing an exceptionally high Ag content in the alloy. Alloy compositions can still be controlled by adjusting the ion concentration ratio of Pd^2＋ and Ag＋ and the electrodeposition processes. XRD shows that nanowires obtained are in the form of alloy of Pd and Ag.     

Precipitation of icosahedral quasicrystalline phase in metallic Zr65Al7.5Ni5Cu17.5Re5 glass

Recently, the precipitation of an icosahedral quasicrystalline phase (I-phase) in metallic Zr₆₅Al_7.5Ni₁₀Cu_12.5M₅ (M=Pd, Pt, Au and Ag) glasses, which were obtained by adding noble metals to the well-known metallic Zr₆₅Al_7.5Ni₁₀Cu_17.5 glass, was reported. In the present work, the crystallization process of a metallic Zr₆₅Al_7.5Ni₅Cu_17.5Re₅ glass, which was obtained by adding non-noble metal Re to Zr₆₅Al_7.5Ni₁₀Cu_17.5, was studied. Two exothermic peaks were observed in the differential scanning calorimetry curve of the metallic glass, of which the low temperature one corresponds to the precipitation of an I-phase. The present result demonstrates that the addition of Re is effective in promoting the precipitation of I-phase, in addition to the previously reported noble metals (Pd, Pt, Au and Ag). The atomic radii of these elements are limited to the range of 0.137 to 0.144 nm, implying that atomic size is a significant factor.     

General synthesis of sponge-like ultrafine nanoporous metals by dealloying in citric acid

A general method is proposed to synthesize ultrafine nanoporous Cu,Ag,and Ni with novel sponge-like morphologies,high porosities,and large surface areas.The materials are produced by dealloying Mg65M25Y10 (M =Cu,Ag,and Ni) metallic glasses in citric acid.Citric acid played a key role due to its capping effect,which reduced the surface diffusion of metals.A structural model consistent with the sponge-like morphology was constructed to calculate the porosity and the surface area.The mechanism of the dealloying process in dtric add,involving ligament formation and coarsening,was illustrated.The mechanism was capable of explaining the experimental trends of dealloying,especially the morphology.A glucose sensor,which can be further developed into a high-precision real-time glucose monitor for medical use,was constructed using sponge-like nanoporous copper.Our findings are not only relevant to understanding the dealloying mechanism of metallic glasses,but also provide promising materials for multiple applications.