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Trace detection of chiral molecules, which is of great significance in chemical, biological, medical, and pharmaceutical sciences, requires microscopic techniques at single-particle or -molecule level. Although ensemble experiments show the...

Instability problems encountered by Ag nanocrystals largely limit their use in practical applications. In AuAg bimetallic alloys, the stability of Ag can be greatly enhanced, whereas doping a high fraction of Au to the alloy usually leads to the loss of the superior properties of Ag and undesirable degradation of the quality factor of the plasmonic resonance. Herein, we provide experimental evidence that the atomically homogenous AuAg alloy nanocrystals with Au fraction as low as 4.9% (at%) possess comparable stability to pure Au, while the superior plasmonic properties of Ag are largely reserved. The study is based on the synthetic strategy developed for the overgrowth on the Au nanorods of atomically homogenous AuAg alloy shells with a tunable Au/Ag ratio but constant size and anisotropic shape. The stability of over 800 individual alloy nanocrystals in the absence of surfactants is simultaneously characterized at the single-particle level for over 10 h under light irradiation. The stability transition is explained in correlation with the charge redistribution of Ag occurring at the same critical Au fraction. We note that such bimetallic alloy nanocrystals with a low Au fraction possessing both high stability and high quality of resonance are preferred in fundamental researches and practical applications.

Reversible redox reaction-based thermochromism using plasmonic nanocrystals is challenging due to the requirements set based on the complexity of the reaction system where the oxidizing and reducing agents must not interfere with each other, and both should possess temperature sensitivity. Herein, we demonstrate plasmonic thermochromism based on a reversible redox reaction of Ag+/Ag on Au nanorods (AuNRs) by incorporating temperature-sensitive reducing and oxidizing agents into the same system. The competition between reduction and oxidation is solely dependent on temperature. When the temperature is above (below) the transition temperature, the reduction of Ag+ (oxidation of Ag) dominates on the surface of AuNRs, and the thermochromic nanostructure solution appears green (red). An experimental study on the mechanism reveals that HOCl produced at low concentrations by H2O2 is the source of the observed temperature dependence of the Ag oxidation. Rationally tuning the transition temperature in a range from 27 to 40 °C can be realized by changing the concentration of some key chemical compounds in the solution. The thermochromic solution can be standalone-functional within multiple cycles of heating and cooling and long-term storage without any additional reagents. Our study provides new insight into plasmonic thermochromism and may pave the way for fabricating smart thermochromic materials.

Reversible redox reaction-based thermochromism using plasmonic nanocrystals is challenging due to the requirements set based on the complexity of the reaction system where the oxidizing and reducing agents must not interfere with each other, and both should possess temperature sensitivity. Herein, we demonstrate plasmonic thermochromism based on a reversible redox reaction of Ag+/Ag on Au nanorods (AuNRs) by incorporating temperature-sensitive reducing and oxidizing agents into the same system. The competition between reduction and oxidation is solely dependent on temperature. When the temperature is above (below) the transition temperature, the reduction of Ag+ (oxidation of Ag) dominates on the surface of AuNRs, and the thermochromic nanostructure solution appears green (red). An experimental study on the mechanism reveals that HOCl produced at low concentrations by H2O2 is the source of the observed temperature dependence of the Ag oxidation. Rationally tuning the transition temperature in a range from 27 to 40 °C can be realized by changing the concentration of some key chemical compounds in the solution. The thermochromic solution can be standalone-functional within multiple cycles of heating and cooling and long-term storage without any additional reagents. Our study provides new insight into plasmonic thermochromism and may pave the way for fabricating smart thermochromic materials.

We demonstrate a CTAB-templated approach towards direct coating of mesoporous titania on gold nanorods in aqueous solutions. The formation of the mesoporous shell is found to be closely correlated with CTAB concentration and the amount of the titania precursor. This approach can be readily extended to form mesoporous titania shells on other CTAB-capped nanoparticles.

We developed a facile approach toward hybrid AgNP-graphene-AgNP sandwiched structures using self-organized monolayered AgNPs from wet chemical synthesis for the optimized enhancement of the Raman response of monolayer graphene. We demonstrate that the Raman scattering of graphene can be enhanced 530 fold in the hybrid structure. The Raman enhancement is sensitively dependent on the hybrid structure, incident angle, and excitation wavelength. A systematic simulation is performed, which well explains the enhancement mechanism. Our study indicates that the enhancement resulted from the plasmonic coupling between the AgNPs on the opposite sides of graphene. Our approach towards ideal substrates offers great potential to produce a "hot surface" for enhancing the Raman response of two-dimensional materials.

Iron oxides are directly coated on the surface of cetyl-trimethylammonium bromide (CTAB)-capped gold nanorods (AuNRs) in aqueous solutions at room temperature, which results in AuNR@Fe2O3, AuNR@Fe3O4, and AuNR@Fe2O3@Fe3O4 core-shell heterostructures. The iron oxide shells are uniform, smooth, with characteristic porous structure, and their thickness can be readily tuned. The shell formation is highly dependent on the reaction parameters including pH and CTAB concentration. The Fe2O3 shell is amorphous and exhibits nearly zero remanence and coercivity, while the Fe3O4 shell is ferromagnetic with a low saturation magnetization of about 0.5 emu g-1 due to its low crystallinity and the porous structure. At elevated temperatures achieved by plasmonic heating of the Au core, the Fe2O3 shell transforms from amorphous to γ-Fe2O3 and α-Fe2O3 phases, while the Fe3O4 phase disappears because of the oxidation of Fe2+. A 1.4-fold increase of photocatalytic performance is observed due to the plasmonic resonance provided by the Au core. The photocatalytic efficiency of Fe3O4 is about 1.7-fold higher than Fe2O3 as more surface defects are present on the Fe3O4 shell, promoting the adsorption and activation of reagents on the surface during the catalytic reactions. This approach can be readily extended to other nanostructures including Au spherical nanoparticles and nanostars. These highly uniform and multifunctional core-shell heterostructures can be of great potential in a variety of energy, magnetic, and environment applications.

"Hot spots" - a kind of highly active site, which are usually composed of some unique units, such as defects, interfaces, catalyst particles or special structures - can determine the performance of nanomaterials. In this paper, we study a model system, i.e. "hot spots" on a single Ag nanowire in the galvanic replacement reaction (GRR), by dark-field microscopy. The research reveals that electric charge can be released by the formation reaction of AgCl, and consequently the electrochemical potential on Ag nanowire drops. The electric charge could induce the reduction of Ag(+) to form the "hot spots" on the nanowire during the GRR. The appearance probability of "hot spots" is almost even along the Ag nanowire, while it is slightly lower near the two ends. The spatial distance between adjacent "hot spots" is also controlled by the charge, and obeys a model based on Boltzmann distribution. In addition, the distance distribution here has an advantage in electron transfer and energy saving. Therefore, it's necessary to consider the functions of electric charge during the synthesis or application of nanomaterials.

Circular dichroism (CD) studies on single nanostructures can yield novel insights into chiroptical physics that are not available from traditional ensemble-based measurements, yet they are challenging because of their weak signals. By introducing an oblique excitation beam, we demonstrate the observation and spectroscopic analysis of a prominent plasmonic chiroptical response from a single v-shaped gold nanorod dimer nanostructure. We show that circular differential scattering from the obliquely excited gold nanorod dimer yields a characteristic bisignate peak-dip spectral shape at hybridized energies of the dimer. This chiroptical response can be ascribed to extrinsic chirality which depends on the geometry configurations of the chiral arrangement. Due to strong near-field coupling, the dipole orientations of the hybridized resonance modes can be in favor of the incident circularly polarized light where a maximum g-factor of ∼0.4 is observed. Promising applications of this chiroptical arrangement as a key component can be in electronics, photonics, or metamaterials.