The Fabrication and SERS Performance of Multi-layer Hollow Au-Ag Alloy Nano Urchins Structure-based SERS Fiber Probe

Novel hollow Au Ag alloy nano urchins were synthesized via Ag seeds growth method,and self-assembly coated on the wall and end-tip of silica fiber for fiber probe fabrication.The nano urchins homogeneously distributed on fiber surface because of fiber silanization.The sizes and tip sharpness of the nano-urchins could be controlled by Ag seeds.The elements distribution analysis indicated there was high Ag content in tip-top for better surface enhance Raman scattering performance.The detectable concentration could be as low as 10-8 M using crystal violet molecules as analyte.Moreover,the fiber probes were stable in air,due to Au in the alloy.This fiber probe could be used for low content single molecular analysis.

Au-Ag alloy nanoparticles with tunable cavity for plasmon-enhanced photocatalytic H2 evolution

Au-Ag alloy nanoparticles with different cavity sizes have great potential for improving photocatalytic performance due to their tunable plasmon effect.In this study,galvanic replacement was combined with co-reduction with the reaction kinetics processes regulated to rapidly synthesize Au-Ag hollow alloy nanoparticles with tunable cavity sizes.The position of the localized surface plasmon resonance(LSPR)peak could be effectively adjusted between 490 nm and 713 nm by decreasing the cavity size of the Au-Ag hollow nanoparticles from 35 nm to 20 nm.The plasmon-enhanced photocatalytic H2 evolution of alloy nanoparticles with different cavity sizes was investigated.Compared with pure P25(TiO2),intact and thin-shelled Au-Ag hollow nanoparticles(HNPs)-supported photocatalyst exhibited an increase in the photocatalytic H2 evolution rate from 0.48μmol h^−1 to 4μmol h^−1 under full-spectrum irradiation.This improved photocatalytic performance was likely due to the plasmon-induced electromagnetic field effect,which caused strong photogenerated charge separation,rather than the generation of hot electrons.

Theoretical research on vacuum separation of Au-Ag alloy

To provide an accurate prediction of the product component dependence of temperature and pressure in vacuum distillation and give convenient and efficient guidance for the designing of the process parameters of industrial production, according to the molecular interaction volume model(MIVM), the separation coefficient(β) and vapor-liquid equilibrium composition of Au-Ag alloy at different temperatures are calculated. Combined with the vapor-liquid equilibrium(VLE) theory, the VLE phase diagrams, including the temperature-composition(T-x) and pressure-composition(p-x) diagrams of Au-Ag alloy in vacuum distillation are plotted. The triple points and condensation temperatures of gold and silver vapors are calculated as well. The results show that the β decreases and the contents of gold in vapor phase increase with the distillation temperature increasing. Low pressures have positive effect on the separation of Ag and Au. The difference between the condensation temperatures of gold and silver is about 450 K in the pressure range of 1-10 Pa.

ZnO nanorod decorated by Au-Ag alloy with greatly increased activity for photocatalytic ethylene oxidation

In recent years, the preservation of fruits and vegetables in cold storage has become an issue of increasing concern, ethylene plays a leading role among them. We found ZnO has the effect of degrading gaseous ethylene, however its effect is not particularly satisfactory. Therefore, we used simple photo-deposition procedure and low-temperature calcination method to synthesize Au, Ag, and Au Ag alloy supported ZnO to improve the photocatalytic efficiency. Satisfactorily, after ZnO loaded with sole Au or Ag particles, the efficiency of ethylene degradation was 17.5 and 26.8 times than that of pure ZnO, showing a large increase in photocatalytic activity. However, the photocatalytic stability of Ag/ZnO was very poor, because Ag can be easily photooxidized to Ag2O. Surprisingly, when ZnO was successfully loaded with the Au Ag alloy, not only the photocatalytic activity was further improved to 94.8 times than that of pure ZnO, but also the photocatalytic stability was very good after 10 times of cycles. Characterization results explained that the Au-Ag alloy NPs modified ZnO showed great visible-light absorption because of the surface plasmon resonance(SPR) effect. Meanwhile, the higher photocurrent density showed the effective carrier separation ability in Au Ag/ZnO. Therefore, the cooperative action of plasmonic Au Ag bimetallic alloy NPs and efficient carrier separation capability result in the outstanding photoactivity of ethylene oxidation. At the same time, the formation of the alloy produced a new crystal structure different from Au and Ag, which overcomes the problem of poor stability of Ag/ZnO, and finally obtains Au Ag/ZnO photocatalyst with high activity and high stability. This work proposes a new concept of using metal alloys to remove ethylene in actual production.

多孔铂镍空心纳米球/石墨烯复合材料的制备

采用置换反应,以镍纳米球为模版和还原剂,以聚二烯丙基二甲基氯化铵为稳定剂制备了多孔铂镍空心纳米球。为了防止空心纳米球之间的团聚,将制备的多孔铂镍空心纳米球与氧化石墨烯混合,然后将氧化石墨烯还原从而制备了铂镍纳米空心球/石墨烯复合材料。

Improved electrochemical performance of ternary Sn-Sb-Cu nanospheres as anode materials for lithium-ion batteries

Ternary Sn-Sb-Cu alloy nanoparticles were successfully synthesized via co-reduction of metal chlorides in aqueous alkaline solution.The results of the transmission electron microscopy(TEM)show that the as prepared Sn-Sb-Cu nanoparticles have a specific hollow structure with a uniform particle size of 10-20 nm.As there are not any hard templates in the synthesis system,a galvanic displacement reaction mechanism is proposed to account for the formation of the hollow nanostructures.When the alloy powders are used as anode materials for lithium-ion batteries,they exhibit relatively high electrochemical capacity and good cyclic retention.The good electrochemical performance can be attributed to the inactive Cu species.During electrochemical reactions,the inactive copper phase in the hollow structure serves as a soft and ductile matrix,which alleviates the mechanical stresses caused by the severe volume change during lithium insertion and extraction.With their high reversible capacities,the Sn-Sb-Cu alloys are a promising candidate as the anode material of rechargeable lithium-ion batteries.

Surface micro/nanostructure evolution of Au-Ag alloy nanoplates： Synthesis, simulation, plasmonic photothermal and surface-enhanced Raman scattering applications

This study reports the controllable surface roughening of Au-Ag alloy nanoplates via the galvanic replacement reaction between single-crystalline triangular Ag nanoplates and HAuC14 in an aqueous medium. With a combination of experimental evidence and finite element method （FEM） simulations, improved electromagnetic field （E-field） enhancement around the surface-roughened Au- Ag nanoplates and tunable light absorption in the near-infrared （NIR） region （-800-1,400 nm） are achieved by the synergistic effects of the localized surface plasmon resonance （LSPR） from the maintained triangular shape, the controllable Au-Ag alloy composition, and the increased surface roughness. The NIR light extinction enables an active photothermal effect as well as a high photothermal conversion efficiency （78.5%）. The well-maintained triangular shape, surface- roughened evolutions of both micro- and nanostructures, and tunable NIR surface plasmon resonance effect enable potential applications of the Au-Ag alloy nanoplates in surface-enhanced Raman spectroscopic detection of biomolecules through 785-nm laser excitation.

Engineering porous architectures in multicomponent PdCuBP mesoporous nanospheres for electrocatalytic ethanol oxidation

Porous features of mesoporous metal nanocrystals are critically important for their applications in catalysis,sorption,and biomedicine and bioimaging.However,precisely engineering porous architectures of mesoporous metals is still highly challenging.Herein,we report a facile soft-templating strategy to precisely engineer porous architectures of multicomponent PdCuBP mesoporous nanospheres(MSs)by using the surfactants with different amphiphilic features.Three kinds of MSs with distinct porous architectures,including three-dimensional(3D)opened/interconnected dendritic mesopores(dMSs),one-dimensional(1D)cylindered mesopores(cMSs),and zero-dimensional(0D)spherical mesopores(sMSs),are prepared.This surfactant-templating method is generally extended to regulate elemental compositions of multicomponent MSs.The resultant Pd-based MSs have been evaluated as the electrocatalysts for ethanol oxidation reaction(EOR).Our results show that quaternary PdCuBP dMSs display remarkably high catalytic activity and better stability for electrocatalytic EOR,compared to those of multicomponent MSs with other porous architectures and less elemental compositions.Mechanism studies reveal that PdCuBP dMSs combine multiple structural and compositional advantages,which kinetically accelerate the electron/mass transfers and also improve the tolerances to poisoning intermediates.We believe that the porous architecture engineering in mesoporous metal electrocatalysts will present a new way to design highly efficient electrocatalysts with desired porous systems and explore their relations towards(electro)catalysis.

Effective fabrication of porous Au-Ag alloy nanorods for in situ Raman monitoring catalytic oxidation and reduction reactions

Porous metal nanostructures exhibit excellent catalytic properties due to their high surface-to-volume ratios and abundant catalytic active sites. However, it is still challenging to control nanopores density and structural features in a facile route and the preparation of porous alloy nanorods for catalytic application has not been well explored. In this work, we demonstrate a synthetic strategy to fabricate highly porous Au–Ag alloy nanorods(P-Au Ag NRs) by critically dealloying Ag atoms from homogeneous solid Au–Ag alloy nanorods(Au Ag NRs). Combining the merits of the tunable plasmonic properties of noble metal nanorods, excellent stabilities of alloys, and superior catalytic activities of porous structures, we use the P-Au Ag NRs as a Raman probe for the in situ monitoring of the catalytic oxidation of 3,3',5,5' tetramethylbenzidine(TMB) and reduction of 4-nitrothiophenol(4-NTP). We also compare their compositiondependent catalytic activities. The results show that P-Au Ag NRs possess superior chemical stability and higher catalytic activity than those of core-shell structures due to synergistic structural and chemical mechanisms. This strategy provides a predictive design approach for the next-generation alloy catalysts with high-performance.

基于消光法反演单分散Au-Ag合金纳米球的粒径和浓度

基于Mie理论分析单分散Au-Ag合金纳米球消光特性随粒径和波长的变化情况。在理论计算中,根据金属纳米颗粒中自由电子平均自由程的缩短效应对Au-Ag合金纳米颗粒的介电函数进行修正。基于消光特性提出了三种确定粒径和浓度的拟合公式,包括共振波长法、双波长消光法和改进的双波长消光法。结果表明,只要测得颗粒的消光谱,就能利用拟合公式反演颗粒的粒径和浓度。此外,对比三种方法的灵敏度和粒径范围发现,相比其他方法,共振波长法的原理更简单、速度更快。

Enzyme-amplified SERS immunoassay with Ag-Au bimetallic SERS hot spots

Surface-enhanced Raman scattering(SERS)enables rapid detection of single molecules with high specificity.However,quantitative and sensitive SERS analysis has been a challenge due to the lack of reliable SERS-active materials.In this study,we developed a quantitative SERS-based immunoassay using enzyme-guided Ag growth on Raman labeling compound(RLC)-immobilized gold nanoparticle(Au NP)-assembled silica NPs(SiO2@Au-RLC@Ag).The enzyme amplified Ag+reduction as well as Ag growth on the RLC-immobilized Au NP-assembled silica NPs(SiO2@Au-RLC),which resulted in a significant increase in SERS signal.In the presence of target antigens such as immunoglobulinG(IgG)or prostate-specific antigen(PSA),Ab1-Antigen-Ab2 immune complex with alkaline phosphatase triggered an enzyme-catalyzed reaction to convert 2-phospho-L-ascorbic acid(2-phospho-L-AA)to ascorbic acid(AA).As produced AA reduced Ag+to Ag,forming an Ag hot spot on the surface of SiO2@Au-RLC,which enhanced the SERS signal of SiO2@Au-RLC@Ag in a solution with a target antigen concentration.The plasmonic immunoassay for IgG detection showed a high linearity of SERS intensity in the range of 0.6 to 9.0 ng/mL with a detection limit(LOD)of 0.09 ng/mL,while an LOD of 0.006 ng/mL was obtained for PSA.The results indicate that the sensitivity of our novel SERS-based immunoassay is higher than that of conventional enzyme-based colorimetric immunoassays.

ZOL-NPs多孔钛合金支架的构建及其载药缓释规律研究

目的研究新型唑来膦酸-纳米微球(ZOL-NPs)多孔钛合金支架的构建方法及其载药释放规律。方法采用计算机辅助设计和电子束熔融(CAD/EBM)技术制备多孔钛合金支架,采用改良二次凝聚法制备明胶纳米微球,复合唑来膦酸、明胶纳米微球、多孔钛合金支架构建ZOL-NPs多孔钛合金支架,并进行生物力学、载药量、载药释放测试。结果制备的明胶纳米微球在水溶液中粒径为(269.5±84.6)nm,粒径表现呈正态分布。扫描电子显微镜下观察到ZOL-NPs均匀复合于支架表面及孔隙内。ZOL-NPs多孔钛合金支架的弹性模量为1.85 GPa,总载药量为(0.285±0.038)μmol,载药率为71.3%。ZOL-NPs多孔钛合金支架第1天体外药物释放量达到总载药量的10%左右,第2天开始药物释放量趋于平稳,缓慢均匀释放,第2天至第28天释放总载药量的29%左右,药物释放周期超过1个月。结论新型ZOL-NPs多孔钛合金支架有效解决了普通金属置入物弹性模量与人体不匹配的问题,载药率高,具有良好体外缓释作用。