Probing nanocolumnar silver nanoparticle/zinc oxide hierarchical assemblies with advanced surface plasmon resonance and their enhanced photocatalytic performance for formaldehyde removal

Recent advances in photocatalysis focus on the development of materials with hierarchical structure and on the surface plasmon resonance (SPR) phenomenon exhibited by metal nanoparticles (NPs). In this work, both are combined in a material where size‐controllable Ag‐NPs are uniformly loaded onto the hierarchical microporous and mesoporous and nanocolumnar structures of ZnO, resulting in Ag‐NP/ZnO nanocomposites. The embedded Ag‐NPs slightly decrease the hydrophobicity of fibrous ZnO, improve its wettability, and increase the absorption of formaldehyde (H₂CO) onto the photocatalyst, all of this resulting in excellent photodegradation of formaldehyde in aqueous solution. Besides, we found that Ag‐NPs with optimal size not only accelerate the charge transfer to the surface of ZnO, but also strengthen the SPR effect in the intercolumnar channels of fibrous ZnO particles combining with high concentration of photo‐generated radical species. The micro‐to‐mesoporous ZnO is like a nanoarray packed Ag‐NPs. With Ag‐NPs of diameter 2.5 < ? < 6.5 nm, ZnO exhibits the most superior photodegradation rate constant value of 0.0239 min^?1 with total formaldehyde removal of 97%. This work presents a new feasible approach involving highly sophisticated Ag‐NP/ZnO architecture combining the SPR effect and hierarchically ordered structures, which results in high photocatalytic activity for formaldehyde photodegradation.     

Elongated hexagonal ZnO micro-fence optical resonator

A highly symmetric ZnO micro-fence is prepared to form an optical resonator, which a symmetric array consisting of six elongated hexagonal microcolumns. It is found that the luminescence emission could be enhanced at the edge of ZnO micro-fence and the wavelength dependent light intensity could be influenced by its geometry. The optical characterization along with theoretical calculations and computer simulation analysis suggest that the Fabry-Perot and Cross-whispering gallery modes are generated in ZnO micro-fence. The individual ZnO micro-fence can regarded as an optical resonator structure. Furthermore, it is proposed that the source concentration around the substrate during the growth is a crucial factor for forming such a micro-fence.     

Catalyst‐Free GaN Nanorods Synthesized by Selective Area Growth

GaN nanorod formation on Ga‐polar GaN by continuous mode metalorganic chemical vapor deposition selective area growth (MOCVD SAG) is achieved under a relatively Ga‐rich condition. The Ga‐rich condition, provided by applying a very low V/III ratio, alters the growth rates of various planes of the defined nanostructure by increasing relative growth rate of the semi‐polar tilted m‐plane {1–101} that usually is the slowest growing plane under continuous growth conditions. This increased growth rate relative to the non‐polar m‐plane {1–100} and even the c‐plane (0001), permits the formation of GaN nanorods with nonpolar sidewalls. In addition, a new growth mode, called the NH₃‐pulsed mode, is introduced, utilizing the advantages of both the continuous mode and the lower growth rate pulsed mode to form nanorods. Finally, nanorods grown under the different growth modes are compared and discussed.     

Interconnectivity between Surface Reactivity and Self-Assembly of Kemp Elimination Catalyzing Nanorods

Understanding the fundamental facts behind dynamicity of catalytic processes has been a longstanding quest across disciplines. Herein, we report self-assembly of catalytically active gold nanorods that can be regulated by tuning its reactivity towards a proton transfer reaction at different pH. Unlike substrate-induced templating and co-operativity, the enhanced aggregation rate is due to alteration of catalytic surface charge only during reactivity as negatively charged transition state of reactant (5-nitrobenzisoxazole) is formed on positively charged nanorod while undergoing a concerted E2-pathway. Herein, enhanced diffusivity during catalytic processes might also act as an additional contributing factor. Furthermore, we have also shown that nanosized hydrophobic cavities of clustered nanorods can also efficiently accelerate the rate of an aromatic nucleophilic substitution reaction, which also demonstrates a catalytic phenomenon that can lead to cascading of other reactions where substrates and products of the starting reactions are not directly involved.     

Spatially-resolved cathodoluminescence spectroscopy of ZnO defects

Spatially-resolved cathodoluminescence spectroscopy has contributed significant new information to our understanding of native point defects in ZnO micro- and nanoscale structures. This paper aims to review representative examples of this work and the new perspectives gained from spatially resolving these defects both laterally and depth-wise. Results obtained from many groups worldwide include studies of Schottky diodes, polycrystalline ceramics, nanostructures, and microwires. The nature and spatial distribution of native point defects in these materials together with their strong dependence on growth and processing suggest new avenues for their control in transport and optoelectronic device structures.     

In-situ deposition of zinc oxide nanowires onto UV-cured chitin derivatives and their antibacterial properties

ZnO nanowires were synthesized on UV-cured chitin film by using a hydrothermal method. Structural and optical characterization showed that one dimensional nanowires can be produced on the UV-cured chitin film. The morphological analysis indicated that nanowires structures can be obtained at about 30 nm radius and 10 µm length. Surface morphology of the ZnO coated UV-cured chitin film was also investigated and a three-dimensional surface profile and high surface roughness were obtained. X-ray diffraction analysis of the film showed large and pure crystals of ZnO nanowires with wurtzite structure and UV–visible absorbance spectrum indicated that ZnO nanowires have 3.39 eV band-gap energy and nanostructures have very good transparency of about 80% in blue region. Also ZnO coated film was tested for its biocidal action against Gram positive Staphylococcus aureus using an agar plate method. This newly developed nano-biomaterial exhibited a strong antibacterial effect.     

Formation of Zn- and O- vacancy clusters in ZnO through deuterium annealing

Open volume defects, clearly distinguishable from the isolated Zn-vacancy are observed in hydrothermally grown ZnO after exposure to deuterium gas at elevated temperatures. From a combination of secondary ion mass spectrometry (SIMS), positron annihilation spectroscopy (PAS) and density functional theory (DFT) calculations it is found that as a result of this treatment vacancy clusters consisting of minimum one Zn- and one O-vacancy are formed, in contrast to introduction of isolated O-vacancies. A scenario for the cluster formation is proposed, where Zn- and O-vacancies originate from the bulk of the sample and the sample surface, respectively. A fraction of the vacancy clusters are decorated by Li and/or H and may therefore be indirectly observed by SIMS. The peak in Li-concentration at about 100 nm below the sample surface, as observed by SIMS is in good correspondence with the PAS-results.     

Effect of low energy proton beam irradiation on structural and electrical properties of ZnO:Al thin films

In this study, we report the structural modification and change in electrical behaviour of aluminium doped zinc oxide by low energy (100 keV) proton irradiation. Aluminium doped zinc oxide films were deposited using DC magnetron sputtering and then annealed for a short duration at 600 °C before irradiation. Structural and defect studies of the films carried out using XRD and Raman spectroscopy. It suggests that the crystalline ordering increases at higher fluences due to annealing of defects in the film. The increase in crystallinity at higher fluences decreases the grain boundary scattering and causes low resistivity. There is no significant change in carrier concentration after the irradiation, however the mobility and resistivity of the Al doped ZnO films change with proton irradiated fluences. The development of defect due to irradiation has been confirmed through Raman spectroscopic studies. The increase in activation energy of particles has been suggested by low energy proton irradiations at higher fluences in the annealed Al doped ZnO thin films. The uniform particle distribution increases with fluences of the irradiation that may be helpful for spintronics and sensor device technology.     

The effects of Zn vacancies on ferromagnetism in Cu-doped ZnO films controlled by oxygen pressure and Li doping

Zn0.99Cu0.01O films were studied experimentally and theoretically.The films were prepared by pulsed-laser deposi tion on Pt(111)/Ti/SiO2/Si substrates under various oxygen pressures to investigate the growth-dependence of the ferromag netic properties.The structural,magnetic,and optical properties were studied,and it was found that all the samples possess a typical wurtzite structure,and that the films exhibit room-temperature ferromagnetism.The sample deposited at 600℃and an oxygen pressure of 10 Pa showed a large saturation magnetization of 0.83μB/Cu.The enhanced ferromagnetism in the(Cu,Li)-codoped ZnO is attributable to the existence of Zn vacancies(VZn),as shown by first-principles calcu lations.The photoluminescence analysis demonstrated the existence of V Zn in both Zn0.99Cu0.01O and(Cu,Li)-codoped ZnO thin films,and this plays an important role in the increase of ferromagnetism,according to the results of first-principles calculations.