A weak acid selective etching strategy was put forward to fabricate oxide-based hollow nanoparticles (HNPs) using core/shell nanostructures of active metal/oxide nanoparticles as sacrificial templates. ZnO-based HNPs, including pure ZnO, Au/ZnO, Pt/ZnO, and Au/Pt/ZnO HNPs with diameter below 50 nm and shell thickness below 6 nm has been first achieved at low temperature. The diameter, thickness, and even sizes of ZnO and noble metal ultrafine crystals of HNPs can be well adjusted by the etching process. Synchronous with the formation of HNPs, the internal metal-semiconductor interfaces can be controllably eliminated (Zn-ZnO) and reconstructed (noble metal-ZnO). Excitingly, such microstructure manipulation has endued them with giant improvements in related performances, including the very strong blue luminescence with enhancement over 3 orders of magnitude for the pure ZnO HNPs and the greatly improved photocatalytic activity for the noble metal/ZnO HNPs. These give them strong potentials in relevant applications, such as blue light emitting devices, environment remediation, drug delivery and release, energy storage and conversion, and sensors. The designed fabrication procedure is simple, feasible, and universal for a series of oxide and noble metal/oxide HNPs with controlled microstructure and improved performances.
We present composition-controlled synthesis of ZnO-Zn composite nanoparticles by laser ablation of a zinc metal target in pure water or in aqueous solution of sodium dodecyl sulfate (SDS). By SDS concentration, composition and size of the nanoparticles can be controlled in a wide range. Relative amounts of the components Zn and ZnO, the particle size, and the microstructure can evolve with SDS concentration in solution. High SDS concentration corresponds to high relative amount of Zn nanoparticles existing as the core in the core/shell nanostructures, whereas low SDS concentration leads to high ZnO amount. This was explained by a dynamic mechanism on the basis of the competition between aqueous oxidation and SDS capping protection. Correspondingly, optical absorption spectra evolve from the excitonic peak of ZnO (about 350 nm) to the Zn surface plasmon resonance (about 242 nm) with rise of SDS concentration. A blue (about 450 nm) photoluminescence was observed in the obtained ZnO nanoparticles, which was attributed to existence of interstitial zinc in ZnO lattices. This study has revealed that laser ablation of active metal in liquid media is an appropriate method to synthesize a series of metal oxide semiconductor-metal composite nanoparticles with controlled composition and size.
A strong violet photoluminescence (PL) band at 425nm (2.92eV) was observed from the ZnO shell layer of the Zn∕ZnO core-shell nanoparticles prepared by laser ablation in liquid media. Such violet PL decreases with increase of the shell thickness or annealing temperature, showing good controllability. Based on the electron paramagnetic resonance measurements, the violet emission is attributed to the electronic transition from the defect level, corresponding to high-concentration zinc interstitials, to the valence band. This study is in favor to clarify the defect-related emissions and to extend the optical and electronic applications of nanostructured ZnO.
The microstructure of the Zn/ZnO core/shell nanoparticles synthesized by laser ablation in liquid medium can be facilely controlled. With the surfactant concentration increased over the critical micelle concentration, the nanoparticle transformed from pure ZnO to a Zn/ZnO core/shell structure. Further, with a decrease of the applied laser power, the ZnO shell thickness was monotonously reduced till 2.5 nm and the ultrafine ZnO nanocrystals embedded in the nanoshells were also reduced till 1.5 nm, which induced the increase of the disorder degree of the nanoshell lattice. The controlling mechanism was discussed according to the competition of capping protection and the oxidation reaction of laser-induced plasma. Blue photoluminescence from the ZnO nanoshells was observed. The emission band exhibited abnormal red-blue shift and narrowing with increasing temperature. Such temperature-dependent behaviors can be well described by a localization model involving an interstitial zinc defect center. These results indicate that this method provides a convenient and universal way to obtain various metal/oxide core/shell nanoparticles with controllable microstructure, and it will be beneficial to an understanding of the physical origins of the blue emission in nanostructured ZnO as well as to extending its optical and electronic applications.
Composite Pt/ZnO porous nanocages with ultrathin porous ZnO shell layers and ultrafine embedded Pt nanoparticles were facilely fabricated by ultrasonic irradiation-assisted two-step etching of Zn/ZnO core/ shell nanoparticle colloids. The Pt cluster size can be well adjusted by the applied ultrasonic power. These Pt/ZnO nanocages exhibit excellent photocatalytic performance and can be further improved by the control of the embedded noble metal nanoparticles, which can be attributed to the abundant nanoscale Schottky contacts in the Pt-ZnO metal-semiconductor interfaces as well as to the large specific surface area due to the unique porous structure. The selective etching route used here could be of considerable universality for fabrication of a series of noble metal/oxide porous nanostructures as photocatalysts, such as the (Au, Ag, Pt, Pd)/(ZnO, TiO 2 ) system.
Expanding localized surface plasmon resonance (LSPR) properties of colloidal copper nanoparticles by laser ablation in liquid (LAL) operated in ambient conditions were reported. The results may aid the application of copper LSPR in optical catalysis and detection devices.
Surface optical (SO) phonon vibration mode predominant Raman scattering spectra were observed in the range of 545–565cm−1 in metal-semiconductor Zn∕ZnO core-shell structured nanoparticles, prepared by laser ablation of a zinc target in a surfactant aqueous solution. The SO phonon mode exhibits significant size confinement effect. Such SO dominant Raman scattering is attributed to the existence of a large number of disorderly arranged areas among ultrafine ZnO grains formed under the extreme condition of laser ablation. This study demonstrates that the properties of surface phonons can availably reflect some important physical information.
We report the fabrication of FeO nanoparticles by pulse laser ablation of pure iron plate in the poly(vinylpyrrolidone) solutions. It has been found that the particle size can be controlled in a wide range from 45 to 5 nm by the surfactant concentration from 0.01 to 0.2 M. The optical absorption measurements of the obtained colloidal solutions show that the optical absorption edge red shifts with reduction of the particle size and exhibits the optical features of the semiconductor with indirect band gap. The red shift is attributed to lattice defects in the nanoparticles. This study shows that pulse laser ablation in liquid media is a good method to synthesize some nanoparticles with special structures, which are difficult to produce by other conventional methods.
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