Enhanced thermal stability of laccase immobilized on monolayer-modified nanoporous Au

Nanoporous Au was fabricated by the dealloying of Au-Ag alloy in nitric acid, and was modified with a self-assembled monolayer (SAM) of 4-aminothiophenol, for the enhancement of high-temperature activity of immobilized laccase. Immobilized laccase exhibited much higher activity than that of free laccase at > 45 °C. SAM surface modification greatly improved the thermal stability and reusability of immobilized laccase. For example, little degradation in laccase activity when immobilized on SAM-modified nanoporous Au was observed after 2 h incubation at 50 °C. This suggested the nanoporous structure and SAM synergistically prevented the conformational change of laccase, and resulted in the enhancement of high-temperature activity.     

Synthesis of Au-Ag alloy nanoparticles with Au/Ag compositional control in SiO2 film matrix

Au-Ag alloy nanoparticles with tunable atomic ratios have been generated in SiO2 film matrix using a new two layer (TL) approach. Two successive overlapping coating layers of similar thickness were deposited on silica glass substrates using Au- and Ag-incorporated inorganic-organic hybrid silica sols, respectively. The Au and Ag concentrations in the individual layers were varied to obtain the desired Au-Ag alloys of different compositions. Four sets of such TL coating assemblies were prepared from the following pair of sols: (i) 4 equivalent mol.% Au-96% SiO2 and 2 equivalent mol.% Ag-98% SiO2, (ii) 3 equivalent mol.% Au-97% SiO2 and 2 equivalent mol.% Ag-98% SiO2, (iii) 3 equivalent mol.% Au-97% SiO2 and 3 equivalent mol.% Ag-97% SiO2, and (iv) 2 equivalent mol.% Au-98% SiO2 and 3 equivalent mol.% Ag-97% SiO2 and subjected to UV (2.75 J/cm2) and heat-treatments (450-550 degrees C) in air and H2-N2 atmospheres for the generation of Au-Ag alloy nanoparticles of approximate compositions Au.66Ag0.33, Au0.6Ag0.4, Au0.5Ag0.5, and Au0.4Ag0.6, respectively. After UV-treatment, individual Au and Ag nanoparticles were formed in the respective layers. The heat-treatment (450-550 degrees C) induces interlayer diffusion of Au and Ag to each other with the generation of Au-Ag alloy nanoparticles, and as a result, Au-Ag alloy surface plasmon resonance (SPR) absorptions were observed in between the Ag- and Au-SPR absorption positions in the visible spectra. The expected alloy compositions are formed through several intermediate alloy nanoparticles, which can also be arrested by controlling the annealing parameters. The alloy formations were monitored by UV-VIS, FTIR, XRD, EDAX, and TEM studies.     

Porous Au–Ag Nanoparticles from Galvanic Replacement Applied as Single-Particle SERS Probe for Quantitative Monitoring

Plasmonic nanostructures have raised the interest of biomedical applications of surface-enhanced Raman scattering (SERS). To improve the enhancement and produce sensitive SERS probes, porous Au–Ag alloy nanoparticles (NPs) are synthesized by dealloying Au–Ag alloy NP-precursors with Au or Ag core in aqueous colloidal environment through galvanic replacement reaction. The novel designed core–shell Au–Ag alloy NP-precursors facilitate controllable synthesis of porous nanostructure, and dealloying degree during the reaction has significant effect on structural and spectral properties of dealloyed porous NPs. Narrow-dispersed dealloyed NPs are obtained using NPs of Au/Ag ratio from 10/90 to 40/60 with Au and Ag core to produce solid core@porous shell and porous nanoshells, having rough surface, hollowness, and porosity around 30–60%. The clean nanostructure from colloidal synthesis exhibits a redshifted plasmon peak up to near-infrared region, and the large accessible surface induces highly localized surface plasmon resonance and generates robust SERS activity. Thus, the porous NPs produce intensely enhanced Raman signal up to 68-fold higher than 100 nm AuNP enhancement at single-particle level, and the estimated Raman enhancement around 7800, showing the potential for highly sensitive SERS probes. The single-particle SERS probes are effectively demonstrated in quantitative monitoring of anticancer drug Doxorubicin release.     

气体吸附诱导Cu(Au)合金中Au原子的偏聚和富集

合金中的表面成分和相偏析会改变其功能,尤其是在表面结构和化学起着至关重要作用的应用中.例如,合金催化剂的表面状态显著影响其在异相催化和电化学过程中的催化性能.表面成分偏析被认为是由表面能的差异驱动,以减少合金体系的总自由能.然而,目前合金中成分偏析的原子尺度进程还尚不清楚,尤其是对于气体分子诱导的成分偏析,在该过程中可能同时发生结构和化学重排.本文通过像差校正环境TEM从原子尺度研究了固溶态Cu(Au)合金在CO气氛下的表面偏析行为. CO气氛能够诱导Cu(Au)合金表面形成有序结构,在很大程度上改变合金的表面化学性质.高温条件下, CO气氛会进一步促进Au原子通过特定的"原子通道"进行扩散,在合金表面偏聚和富集.富集形成的Au纳米颗粒与合金表面在形貌和结构方面发生了丰富的动力学交互作用.这其中CO气体吸附也起着重要的作用.这些原子尺度的研究结果为双金属合金的表面偏析和去合金化机理提供了直接证据,并突出了气体吸附物在这些表面行为中的作用.     

Fabrication of cubic nanocages and nanoframes by dealloying Au/Ag alloy nanoboxes with an aqueous etchant based on Fe(NO3)3 or NH4OH

This paper describes a two-step procedure for generating cubic nanocages and nanoframes. In the first step, Au/Ag alloy nanoboxes were synthesized through the galvanic replacement reaction between Ag nanocubes and an aqueous HAuCl4 solution. The second step involved the selective removal (or dealloying) of Ag from the alloy nanoboxes with an aqueous etchant based on Fe(NO3)3 or NH4OH. The use of a wet etchant other than HAuCl4 for the dealloying process allows one to better control the wall thickness and porosity of resultant nanocages because there is no concurrent deposition of Au. By increasing the amount of Fe(NO3)3 or NH4OH added to the dealloying process, nanoboxes derived from 50-nm Ag nanocubes could be converted into nanocages and then cubic nanoframes with surface plasmon resonance (SPR) peaks continuously shifted from the visible region to 1200 nm. It is also possible to obtain nanocages with relatively narrow SPR peaks (with a full width at half-maximum as small as 180 nm) by controlling the amount of HAuCl4 used for the galvanic replacement reaction and thus the optimization of the percentage of Au in the alloy nanoboxes.     

Bulk gold with hierarchical macro-, micro- and nano-porosity

Millimeter-sized, free-standing gold structures were created with three levels of multiscale porosity. First, macro- and microporosity, which are useful for mass and heat transport within the structure, are formed within an Ag-19 at.% Au alloy by salt powder replication during powder densification and by entrapped gas expansion during sintering, respectively. Nanoporosity, which provides high surface area, is then produced by silver dealloying of these Ag-19 at.% Au foams. The resulting hierarchical gold structures are annealed at 100-800 °C, thus coarsening the ligaments, increasing relative density, and healing cracks produced during dealloying. The first effect weakens the structure, while the other two make it stronger. A bulk Au sample with hierarchical porosity annealed at 600 °C shows good compressive ductility and a strength in agreement with models.     

Robust Synthesis of Gold Cubic Nanoframes through a Combination of Galvanic Replacement,Gold Deposition,and Silver Dealloying

A facile, robust approach to the synthesis of Au cubic nanoframes is described. The synthesis involves three major steps: 1) preparation of Au–Ag alloyed nanocages using a galvanic replacement reaction between Ag nanocubes and HAuCl₄; 2) deposition of thin layers of pure Au onto the surfaces of the nanocages by reducing HAuCl₄ with ascorbic acid, and; 3) formation of Au cubic nanoframes through a dealloying process with HAuCl₄. The key to the formation of Au cubic nanoframes is to coat the surfaces of the Au–Ag nanocages with sufficiently thick layers of Au before they are dealloyed. The Au layer could prevent the skeleton of a nanocage from being fragmented during the dealloying step. The as‐prepared Au cubic nanoframes exhibit tunable localized surface plasmon resonance peaks in the near‐infrared region, but with much lower Ag content as compared with the initial Au–Ag nanocages.     

Facile synthesis of metal and alloy nanoparticles by ultrasound-assisted dealloying of metallic glasses

Metal and alloy nanoparticles synthesized by chemical reduction have attracted increasing attention due to their superior physical,chemical,and biological properties.However,most chemical synthesis processes rely on the use of harsh reducing agents and complicated chemical ingredients.Herein,we report a novel reduction-agent-free and surfactant(stabilizer)-free strategy to synthesize Cu,Ag,Au,Cu-Pt,Cu-Au,Cu-Au-Pt-Pd,and Au-Pt-Pd-Cu nanoparticles by ultrasound-assisted dealloying of Mg-based metallic glasses.The formation mechanism of the metal and alloy nanoparticles is revealed by a detailed investigation of sequential intermediate products.We demonstrate that the glass-liquid phase transition of the initially dealloying metallic glasses,together with the synergistic effect of dealloying and ultrasound-driven ligament-breakage of small enough nanoporous intermediates,play key roles in preparing the uniformly dispersed metal and alloy nanoparticles.This approach greatly simplifies the up-scaling synthesis of monometallic and bimetallic nanoparticles,and also provides a general strategy for synthesizing unprecedented multimetallic nanoparticles.     

电场对Au/SiO_2及Au-Ag/SiO_2表面结构与原子迁移特性的影响

利用扫描俄歇微探针（SAM）和原子力显微镜（AFM）研究了SiO2衬底上在外加直流电场作用下沉积的Au薄膜及Au－Ag复层薄膜的表面形貌、结构变化及电迁移扩散行为。结果表明：①在衬底表面施加水平方向电场辅助沉积制备的Au薄膜其表面显示出平整的椭球形晶粒，并沿外电场方向呈织构取向。与未加电场的热蒸发沉积膜相比，具有较为均匀、有序的表面微观结构。②SiO2表面Au-Ag复层薄膜在直流电场作用下，Au，Ag物种同时向负极方向作走向迁移扩散，这与Au－Ag复层薄膜在Si（111）表面电迁移时Au，Ag分别向两极扩散的特点不同，反映了衬底性质对表面原子电迁移的影响。③Au－Ag复膜在电迁移过程中还发生了表面原子聚集状态的变化，原来沉积排布的细小晶粒在电迁移扩散过程中出现不均匀长大，导致薄膜表面粗糙度显著增加。     

Dealloying by metallic melt

Dealloying, which commonly involves corrosion processes in aqueous solutions, is a promising technique for preparing functional nanoporous metals. While this technique is ideal for preparing nanoporous noble metals such as of Au, it is not readily applicable to less-noble metals. Here, we propose a novel dealloying method employing a metallic melt, instead of an aqueous solution, as the dealloying liquid for a preparing of nanoporous metals. An atomic interaction among alloy components and metallic melt causes specific component to dissolve out from the alloy solid into the melt with self-organizing nanoporous structure by the remaining component. The dealloying method can be applied for preparation of nanoporous less-noble metal such as of Ti for the development of functional materials such as fluid filters, gas absorption media, and biomaterials.     

Necklace-shaped Au-Ag nanoalloys: laser-assisted synthesis and nonlinear optical properties

Here in this paper, necklace-shaped Au-Ag nanoalloys (NAs) have been synthesized by a laser-based approach. A chain of Ag nanoparticles (NPs), which were joined together with Au junctions, was formed upon copper vapor laser (CVL) irradiation of a colloidal mixture of Ag and Au NPs; while the corresponding NPs were separately provided by laser ablation of gold and silver targets in deionized water by a 1064 nm Q-switched Nd:YAG laser. Dependence of the NAs development process on the CVL irradiation time in three distinct stages of as-mixed, nucleation and complete formation has been systematically studied by UV-vis optical absorption spectroscopy analysis as well as by transmission electron microscopy (TEM), which was exploited to visually confirm the NAs evolution through the process. Furthermore, the x-ray photoelectron spectroscopy (XPS) technique was accurately employed to determine the synthesized alloy content. On the other hand, using the open-and closed-aperture Z-scan technique, the nonlinear absorption (NLA) as well as nonlinear refraction (NLR) changes in Au-Ag NAs were investigated through their formation. The deduced results from the nonlinear optical properties of the colloidal NAs in the mentioned stages were interpreted considering the spectroscopic and microscopic observations. The total change of individual Au and Ag NPs saturable absorption (SA) into the reverse saturable absorption (RSA) behavior was concluded through the evolution into Au-Ag NAs.     

Stable Na Plating and Stripping Electrochemistry Promoted by In Situ Construction of an Alloy‐Based Sodiophilic Interphase

Sodium metal anodes are poor due to the reversibility of Na plating/stripping, which hinders their practical applications. A strategy to form a sodiophilic Au–Na alloy interphase on a Cu current collector, involving a sputtered Au thin layer, is shown to enable efficient Na plating/stripping for a certain period of time. Herein, electrochemical behaviors of Na plating on different substrates are explored, and it is revealed that the sodiophilic interphase can be achieved universally by in situ formation of M–Na (M = Au, Sn, and Sb) alloys during Na plating prior to Na bulk deposition in the initial cycle. Moreover, it is found that repetitive alloying–dealloying leads to falling‐off of thin film sodiophilic materials and thus limits the lifespan of efficient Na cycling. Therefore, an approach is further developed by employing particles of sodiophilic materials combined with the control over the cutoff potential, which significantly improves the stability of Na plating/stripping process. Especially, the low‐cost Cu@Sn‐NPs and Cu@Sb‐MPs composite current collectors allow Na plating and stripping to cycle for 2000 and 1700 times with the average efficiency of 99.9% at 2 mA cm^?2.     

Fabrication of nanoporous silver and microstructural change during dealloying of melt-spun Al–20 at.%Ag in hydrochloric acid

Ag nanoporous structure has been fabricated by dealloying of Al–20 at.%Ag in 2 M HCl at room temperature. We describe the changes of phase constitution and microstructural morphology during the dealloying. The bi-phase structure of α-Al and γ-Ag₂Al was obtained using melt-spinning, and considerable amount of γ-Ag₂Al was suppressed. According to the phase quantitative analysis, 5.6 % γ-Ag₂Al was precipitated at the grain boundary and inside the grain. At the early stage of dealloying process, the deep channel occurred at the interface of α-Al and γ-Ag₂Al due to concentration gradient of Ag; and then, α-Al was preferentially dealloyed with comparison to γ-Ag₂Al and formed 3-dimensional nanoporous structure which showed the open-pore/ligament bi-continuous structure. After 720 min, γ-Ag₂Al was dealloyed and formed 2-dimensional pored-wall structure. At the end of dealloying reaction, the initial grain/intermetallic wall structure was maintained. The Ag nanoporous structure was gradually coarsened with the increase of dealloying time, from 25 ± 5 nm at 20 min to 113 ± 22 nm at 720 min. The calculated coefficient of surface diffusion of Ag was 2.34 × 10^?17 m²/s. The surface diffusivity of Ag obtained in this study showed two orders of magnitude higher than the Au dealloyed from Au–Ag precursor at the similar temperature.     

Microstructural damage analysis of SnAgCu solder joints and an assessment on indentation procedures

In solder joint reliability, solder/pad adjoining interface is crucial, the quality of which is determined by the metallization. In this paper, microstructural analyses of SnAgCu alloy and soldered joints are conducted in direct connection with the metallization. Solder balls, solder paste and cast SnAgCu are reflowed on Cu, Ni/Au and Cu/Ni(V)/Au. Substrate influence on bulk and interfacial metallurgy is examined and a correlation between interfacial microstructure and the corresponding damage paths is established. Damage localizes at the bonding interfaces with a strong influence of intermetallic layers and primary crystals. Crack propagation is studied with Cu and Ni/Au substrates and the cracking mechanism in principal directions is scrutinized. In BGA production, different reflow parameters are investigated, and an optimum bumping procedure is established. Nano-indentation is used for the mechanical characterization of the solder alloy. An assessment on indentation parameters for soft solders is conducted and the influence of Ag content on material properties of SnAgCu is presented.     

Role of coarse intermetallic particles on the environmentally assisted cracking behavior of peak aged and over aged Al–Zn–Mg–Cu–Zr alloy during slow strain rate testing

Coarse intermetallic particles (larger than 1 μm in size) in Al–Zn–Mg–Cu–Zr (7010) alloy were found to significantly influence the crack initiation of the over aged alloy while not affecting the more susceptible peak aged alloy, when subjected to slow strain rate testing (SSRT) in 3.5% NaCl solution. A detailed study was undertaken to examine the causes of such an observation. The study shows that the galvanic action and/or dealloying of the coarse intermetallic particles are responsible for the crack initiation in the over aged alloy. However, this phenomenon is not seen in the peak aged alloy due to its inherent environmentally assisted cracking (EAC) susceptibility and the consequent failure in shorter duration, before the coarse particles can exert an influence.     

Failure analysis of brass portions of dielectric unions

Persistent failures (leakage) were observed in the brass portion of dielectric unions after a relatively short service period. Metallographic examination revealed evidence of severe stress-corrosion cracking within the brass as well as dealloying on the surface. Evaluations using stress calculations and the dynamics of freezing water indicated that the unions were not overtightened during installation, and the water passing through the unions did not freeze. The subject copper alloy was shown to have been insufficient for the intended application due to high susceptibility to corrosion.     

去合金化制备具有高循环稳定性的纳米多孔Sb/MCNT储钠负极材料

为提升Sb基负极材料的储钠循环性能, 通过简单的两步法(机械辅助化学合金化和酸溶解去合金化)制备纳米化和多孔化的去合金锑/多壁碳纳米管(De-Sb/MCNT)复合物, 采用不同方法表征材料的物理化学性质和储钠电化学性能。结果显示, De-Sb/MCNT材料的可逆比容量达到408.6 mAh·g^-1 (200 mA·g^-1), 首周库仑效率为69.2%; 在800 mA·g^-1循环330周后, 容量保持率仍可达88%, 展现出优异的储钠循环性能。这得益于机械辅助化学合金化/酸溶解去合金化对商品化Sb的“预粉化”作用, 促进了材料的纳米化和多孔化, 缓解了充放电过程中的体积膨胀, 实现了高的循环稳定性。这种常温合金化/去合金化的方法为制备循环稳定的储钠合金负极材料提供了新的途径。     

Coke formation on nickel-chromium-iron alloys

Coke formation during the steam cracking of propane has been studied on foils of nickel and of a series of nickel-chromium-iron alloys with a nickel content between 8 and 74wt%. The experiments were carried out at 810 and 850° C in a tubular flow reactor. Coke deposition was measured on prereduced foils using a microbalance. After an initial period the rates of coke deposition on the alloy foils tend to approach a common value independent of the nickel content. On the pure nickel foils a substantially higher rate of coke formation was observed. The results can be explained in terms of the surface composition of the foils as measured by Auger electron spectroscopy.     

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。     

Electric field induced interfacial reaction of Au-Ag bimetal film on SiO2 surface

Interface evolution of nanometer scale Au-Ag bimetal film on SiO₂ substrate surface during electromigration was investigated by angle resolved X-ray photoelectronspectroscopy (ARXPS). ARXPS spectra showed that a chemical reaction between Au-Ag filmand SiO₂ layer occurred at interface, which caused Au, Ag and Si having differentdistribution and chemical states across the film. This result as well as previousobservation by atomic force microscopy (AFM) demonstrate that electromigration of Au-Agbimetal film on SiO₂ surface is accompanied with strong interfacial chemicalreaction rather than a simple lateral physical diffusion process.