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.

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.

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.

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.

Au-Ag合金纳米球壳光吸收和后向散射特性的优化

为了找到光吸收和后向散射特性更好的纳米球壳,利用双层同心球的Mie散射理论和介电函数的尺寸修正模型定量分析了Au-Ag合金纳米球壳的内核半径、外壳厚度、合金成分和周围介质对光吸收和后向散射特性的影响。结果表明,当Au的摩尔分数为50%,步距为0.01 nm,内核分别为SiO_(2)和真空情况时,Au-Ag合金纳米球壳的体积吸收系数最大值分别为93.660μm^(-1)和99.316μm^(-1)时,内核半径分别为27.89 nm和28.02 nm,外壳厚度分别为3.95 nm和3.35 nm;后向散射系数的最大值分别为5.280μm^(-1)和5.550μm^(-1)时,内核半径分别为56.08 nm和56.37 nm,外壳厚度分别为10.47 nm和8.89 nm。此外,当Au的摩尔分数小于9%时,Au-Ag合金纳米球壳的光吸收特性优于Au纳米球壳;当Au的摩尔分数小于11%时,Au-Ag合金纳米球壳的后向散射特性优于Au纳米球壳。

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.