Photoluminescence Resulting from Semiconductor−Metal Solid Solution Observed in One-Dimensional Semiconductor Nanostructures

A narrow band photoluminescence (PL) emission peak resulting from CdS−Au solid solution was observed when growing one-dimensional nanostructures of CdS via the vapor−liquid−solid mechanism by using Au as the catalyst. This emission peak was located at 680 nm, a wavelength longer than the near band edge emission of CdS at 520 nm, and was shown not to be caused by the usual trap states of CdS which lead to a broad band emission. Here, the one-dimensional nanostructures of CdS were grown in a simple, low-temperature (360 °C) metal−organic chemical vapor deposition process with a single source precursor of CdS. Straight nanowires of diameter 50−70 nm and wormlike nanorods of diameter 100−200 nm were obtained. Both the upper and lower portions of the nanorods/nanowires possessed single crystallinity as judged from the corresponding high-resolution transmission electron microscopy images and selected area electron diffraction data. This work demonstrates the feasibility of adjusting PL emission peaks of optoelectronic semiconductors through alloying with metals

Au-CdS Core−Shell Nanocrystals with Controllable Shell Thickness and Photoinduced Charge Separation Property

Au-CdS Core−Shell Nanocrystals with Controllable Shell Thickness and Photoinduced Charge Separation Propert

Spontaneous Reduction of Metal Ions Initiated by Ethylenediamine-Capped CdS Nanowires: A Sensing Mechanism Revealed

Spontaneous Reduction of Metal Ions Initiated by Ethylenediamine-Capped CdS Nanowires: A Sensing Mechanism Reveale

ZnSe·0.5N₂H₄ Hybrid Nanostructures: A Promising Alternative Photocatalyst for Solar Conversion

As the molecular precursor of ZnSe, ZnSe·0.5N₂H₄ inorganic–organic hybrids have received relatively less attention due to the feasibility of their further processing and decomposition into pure-phase ZnSe. Here we demonstrated that ZnSe·0.5N₂H₄ hybrid nanostructures, which were prepared using a facile hydrazine-assisted hydrothermal method, may practically harvest solar energy for photoconversion applications. By modulating the volume ratio of hydrazine hydrate to deionized water employed in the synthesis, the morphology of the grown ZnSe·0.5N₂H₄ can be varied, which included nanowires, nanobelts and nanoflakes. With the relatively long exciton lifetime and highly anisotropic structure, ZnSe·0.5N₂H₄ nanowires performed much better in the photodegradation of rhodamine B than the other two counterpart products. As compared to pure ZnSe nanoparticles and single-phase ZnSe nanowires obtained from further processing ZnSe·0.5N₂H₄, the ZnSe·0.5N₂H₄ hybrid nanowires exhibited superior photocatalytic performance under visible light illumination. The hybrid nanowires were further decorated with Au particles to endow them with structural and compositional diversities. Time-resolved photoluminescence spectra suggested that almost 40% of the photoexcited electrons in ZnSe·0.5N₂H₄ nanowires can be transported to the decorated Au, which enabled a fuller extent of participation of charge carriers in the photocatalytic process and thus conduced to a significant enhancement in the photocatalytic activity. The demonstrations from this work illustrate that ZnSe·0.5N₂H₄ hybrid nanostructures can serve as a versatile photocatalyst platform for advanced photocatalytic applications

Triple-Channel Charge Transfer over W₁₈O₄₉/Au/g‑C₃N₄ <i>Z</i>‑Scheme Photocatalysts for Achieving Broad-Spectrum Solar Hydrogen Production

Z-scheme heterojunctions are fundamentally promising yet practically appealing for photocatalytic hydrogen (H2) production owing to the enhanced redox power, spatial separation of charge carriers, and broad-spectrum solar light harvesting. The charge-transfer dynamics at Z-scheme heterojunctions can be accelerated by inserting charge-transfer mediators at the heterojunction interfaces. In this study, we introduce Au nanoparticle mediators in the Z-scheme W18O49/g-C3N4 heterostructure, which enables an improved H2 production rate of 3465 μmol/g·h compared with the direct Z-scheme W18O49/g-C3N4 (1785 μmol/g·h) under 1 sun irradiation. The apparent quantum yields of H2 production with W18O49/Au/g-C3N4 are 3.9% and 9.3% at 420 and 1200 nm, respectively. The improved photocatalytic H2 production activity of W18O49/Au/g-C3N4 is attributable to the triple-channel charge-transfer mechanism: channel IZ-scheme charge transfer facilitates charge separation and increased redox power of the photoexcited electrons; channels II and IIIthe localized surface plasmon resonances from Au (channel II) and W18O49 (channel III) enable light harvesting extension from visible to near-infrared wavelengths

Metal-Particle-Decorated ZnO Nanocrystals: Photocatalysis and Charge Dynamics

Understanding of charge transfer processes is determinant to the performance optimization for semiconductor photocatalysts. As a representative model of composite photocatalysts, metal-particle-decorated ZnO has been widely employed for a great deal of photocatalytic applications; however, the dependence of charge carrier dynamics on the metal content and metal composition and their correlation with the photocatalytic properties have seldom been reported. Here, the interfacial charge dynamics for metal-decorated ZnO nanocrystals were investigated and their correspondence with the photocatalytic properties was evaluated. The samples were prepared with a delicate antisolvent approach, in which ZnO nanocrystals were grown along with metal particle decoration in a deep eutectic solvent. By modulating the experimental conditions, the metal content (from 0.6 to 2.3 at%) and metal composition (including Ag, Au, and Pd) in the resulting metal-decorated ZnO could be readily controlled. Time-resolved photoluminescence spectra showed that an optimal Au content of 1.3 at% could effectuate the largest electron transfer rate constant for Au-decorated ZnO nanocrystals, in conformity with the highest photocatalytic efficiency observed. The relevance of charge carrier dynamics to the metal composition was also inspected and realized in terms of the energy level difference between ZnO and metal. Among the three metal-decorated ZnO samples tested, ZnO–Pd displayed the highest photocatalytic activity, fundamentally according with the largest electron transfer rate constant deduced in carrier dynamics measurements. The current work was the first study to present the correlations among charge carrier dynamics, metal content, metal composition, and the resultant photocatalytic properties for semiconductor/metal heterostructures. The findings not only helped to resolve the standing issues regarding the mechanistic foundation of photocatalysis but also shed light on the intelligent design of semiconductor/metal composite systems to consolidate their utility in photocatalytic fields

Crystal Facet Dependent Energy Band Structures of Polyhedral Cu₂O Nanocrystals and Their Application in Solar Fuel Production

We demonstrated a facile hydrothermal method to synthesize the (100)-, (110)- and (111)-oriented Cu2O nanocrystals (NCs) by controlling the concentration of the incorporated anions (CO32– and SO32–). The crystal facet dependent activity of the orientation controlled Cu2O NCs in the rhodamine B (RhB) photodegradation and photocatalytic hydrogen (H2) evolution was found to follow the trend: (111) > (110) > (100). The mechanism was investigated by characterizing the optical property, energy band structure, interfacial charge carrier dynamics and reducing ability. The results indicated that the (111)-oriented Cu2O NCs exhibit the higher conduction band (CB) potential as compared with the (110)-oriented and (100)-oriented Cu2O NCs, which resulted in the largest driving force of interfacial electron transfer for (111)-oriented Cu2O NCs to carry out solar fuel generation. The current study offers an easy strategy for crystal facet engineering of semiconductors and provides important physical insights into their electronic properties for the desired solar energy conversions

Crystal Facet Dependent Energy Band Structures of Polyhedral Cu₂O Nanocrystals and Their Application in Solar Fuel Production

We demonstrated a facile hydrothermal method to synthesize the (100)-, (110)- and (111)-oriented Cu2O nanocrystals (NCs) by controlling the concentration of the incorporated anions (CO32– and SO32–). The crystal facet dependent activity of the orientation controlled Cu2O NCs in the rhodamine B (RhB) photodegradation and photocatalytic hydrogen (H2) evolution was found to follow the trend: (111) > (110) > (100). The mechanism was investigated by characterizing the optical property, energy band structure, interfacial charge carrier dynamics and reducing ability. The results indicated that the (111)-oriented Cu2O NCs exhibit the higher conduction band (CB) potential as compared with the (110)-oriented and (100)-oriented Cu2O NCs, which resulted in the largest driving force of interfacial electron transfer for (111)-oriented Cu2O NCs to carry out solar fuel generation. The current study offers an easy strategy for crystal facet engineering of semiconductors and provides important physical insights into their electronic properties for the desired solar energy conversions