Controllable synthesis of zinc-substituted alpha- and beta-nickel hydroxide nanostructures and their collective intrinsic properties

A new controllable homogeneous precipitation approach has been developed to synthesize zinc-substituted nickel hydroxide nanostructures with different Zn contents from a zinc nanostructured reactant. As typical layered double hydroxides (LDHs), zinc-substituted nickel hydroxide nanostructures can be formulated as NiZnx(Cl)y(OH)2(1+x)-y.z H2O (x=0.34-0.89, y=0-0.24, z=0-1.36). The structure and morphology of zinc-substituted nickel hydroxide nanostructures can be systematically controlled by adjustment of the zinc content. The effects of temperature and the amounts of ammonia and zinc nanostructured precursor on the reaction were systematically investigated. In our new method, although zinc-substituted alpha-and beta-nickel hydroxides have the typical 3D flowerlike architecture and stacks-of-pancakes nanostructures, respectively, their growth processes are different from those previously reported. A coordinative homogeneous precipitation mechanism is proposed to explain the formation process of zinc-substituted nickel hydroxide nanostructures. The zinc-substituted nickel hydroxide nanostructures exhibit some interesting intrinsic properties, and changing the zinc content can effectively tune their optical, magnetic, and electrical properties.     

A completely green approach to the synthesis of dendritic silver nanostructures starting from white grape pomace as a potential nanofactory

A simple, eco-friendly, cost-effective and rapid microwave-assisted method has been developed to synthetize dendritic silver nanostructures, composed of silver nanoparticles (AgNPs), using white grape pomace aqueous extract (WGPE) as both reducing and capping agent. With this aim, WGPE and AgNO₃ (1 mM) were mixed at different ratio, and microwave irradiated at 700 W, for 40 s. To understand the role of bioactive compounds involved in the green synthesis of AgNPs, preliminary chemical characterization, FT-IR analysis and ¹H NMR metabolite profiling of WGPE were carried out. The effects of bioactive extract concentration and stability over time on AgNPs formation were also evaluated. WGPE-mediated silver nanostructures were then characterized by UV–vis, FTIR analyses, and scanning electron microscopy. Interestingly, the formation of dendritic nanostructures, originated from the self-assembly of Ag rounded nanoparticles (average diameter of 33 ± 6 nm), was observed and ascribed to the use of microwave power and the presence of organic components within the used WGPE, inducing an anisotropic crystal growth and promoting a diffusion-limited aggregation mechanism. The bio-dendritic synthetized nanostructures were also evaluated for potential applications in bio-sensing and agricultural fields. Cyclic voltammetry measurements in 0.5 M phosphate + 0.1 M KCl buffer, pH 7.4 showed that green AgNPs possess the electroactive properties typical of AgNPs produced using chemical protocol. The biological activity of synthetized AgNPs was evaluated by in-vitro antifungal activity against F. graminearum. Additionally, a phytotoxicity evaluation of synthetized green nanostructures was carried out on wheat seed germination. Results highlighted the potential of WGPE as green agent for bio-inspired nanomaterial synthesis, and of green Ag nanostructures, which can be used as antifungal agent and in biosensing applications.     

Green synthesis of catalytic Zinc Oxide nano-flowers and their bacterial infection therapy

Herein, Zinc Oxide nanoflowers (ZnONFs) with low cost, non-hazardous and renewable phytochemicals from plant (Thlaspi arvense) extract were synthesized via facile method under controlled optimized experimental conditions. The as-fabricated Zinc Oxide nanoflowers were comprehensively characterized by UV–visible spectroscopy, Fourier Transform infrared spectroscopy, X-ray diffraction, Scanning electron microscopy, High-resolution transmission electron microscopy, and Energy dispersive spectroscopy techniques. The bio-fabricated Zinc Oxide nanoflowers performed an admirable potential activity against Gram-negative bacterium (Escherichia coli) and significantly inhibited its growth, due to an intracellular generation of reactive-oxygen-species. The photocatalytic performances of as bio-synthesized Zinc Oxide nanoflowers were also tested by reducing 4-nitrophenol and methylene blue. The superior photocatalytic activities of Zinc Oxide nanoflowers are attributed to the high surface area, efficient photogenerated electron and hole separation owing to the capped plant moieties. The as-synthesized Zinc Oxide nanoflowers by green method exhibited a significant antibacterial activity and efficient photocatalytic performances. This synthetic strategy will open a new window for the fabrication of nanomaterial with effective removal of wastewater contaminants and pathogens.     

Oriented morphogenesis of ZnO nanostructures from water-soluble zinc salts under environmentally mild conditions and their optical properties

Herein, we report a bottom-up, mineralization strategy, which borrows key principles from biomineralization processes, to synthesize nanostructured materials. A long-chain polyamine simultaneously mineralizes and assembles ZnO nanoparticles directly from water-soluble zinc salts under sustainable synthesis conditions. These thus-generated oriented structures undergo interesting morphogenesis that is controlled by changing the ratio of polyamine/Zn(2+) ions. As the ratio increases, the morphology changes from a spherical shape to oval-, dumbbell-, and finally hexagonal-rod-shaped structures that contain unique hollow rod structures. Using XPS, XRD, FT-IR, Raman spectroscopy, DLS, and confocal fluorescence microscopic analysis, we elucidate the mechanism of structural evolution; this mechanism involves the initial formation of a zinc/amine complex that is furnished with polyamine chains. These chains facilitate the condensation process to form ZnO nanoparticles and their assembly in aqueous medium at neutral pH. Further, the presence of defects in the thus-morphogenized ZnO structures leads to blue luminescence and efficient photoinduced activity, assisted by the surface-hole-trapping effect of polyamines.     

Green synthesis and characterization of Fe doped ZnO nanoparticles and their interaction with bovine serum albumin

Herein we report an eco-friendly and cost efficient synthesis of Fe doped ZnO (TPFZO) nanoparticles using the extract of Thespesia polpulanea flowers as a stabilizing agent. The synthesized NPs have been characterized by XRD, FT-IR, UV-DRS, SEM, EDAX and TEM studies. The synthesized NPs were found to have the crystallite size in the range of 30–60 ​nm. The calculated band gap energies for ZO and TPFZO nanoparticles were 3.00 ​eV and 1.97 ​eV respectively. The size distribution of the ZO and TPFZO obtained from TEM were observed to be lying in the range 50–120 ​nm and 4–22 ​nm respectively. The interaction of TPFZO NPs with bovine serum albumin (BSA) has been studied using fluorescence and absorption titration methods. The results indicated that the nanoparticles quenched the BSA fluorescence at 340 ​nm via static quenching mode having a bimolecular quenching rate constant value of 6.21 ​× ​10¹³ Lmol⁻¹s⁻¹.     

Effects of the thermal decomposition of surface oxygen species on the chemical and catalytic properties of activated carbon supported Pt catalysts

Several carbon supported Pt catalysts were prepared by varying surface properties of support and tested for methylene chloride oxidation. They were investigated by BET, TPD, pH analysis and XPS. The Pt species would stabilize when the surface carbon was pregraphitized due to the π sites of basal plane. This revised version was published online in June 2006 with corrections to the Cover Date.     

Shape-controlled synthesis of metal nanostructures: the case of silver

The concept of shape-controlled synthesis is discussed by investigating the growth mechanisms for silver nanocubes, nanowires, and nanospheres produced through a polymer-mediated polyol process. Experimental parameters, such as the concentration of AgNO(3) (the precursor to silver), the molar ratio between poly(vinylpyrrolidone) (PVP, the capping agent) and AgNO(3), and the strength of chemical interaction between PVP and various crystallographic planes of silver, were found to determine the crystallinity of seeds (e.g., single crystal versus decahedral multiply twinned particles). In turn, the crystallinity of a seed and the extent of the PVP coverage on the seed were both instrumental in controlling the morphology of final product. The ability to generate silver nanostructures with well-defined morphologies provides a great opportunity to experimentally and systematically study the relationship between their properties and geometric shapes.     

Relationship between ammonia sensing properties of polyaniline nanostructures and their deposition and synthesis methods

The ammonia absorption properties of polyaniline nanostructures are studied in terms of sensitivity, response and recovery times and stability. These characteristics are obtained by measuring, at room temperature, the absorbance variations at 632 nm. The nanostructures are synthesized either by interfacial or rapid or dropwise polymerizations with the oxidant-to-monomer mole ratio equals to 0.5 or 1. The influence of the deposition method (in-situ or drop-coating technique) as well as the nature of the dopant (HCl, CSA or I₂) on the gas detection properties are also studied. The results show a strong dependence of the morphology on the deposition method, the in-situ technique leads to the best sensitivity and response time. For this deposition method, the nanostructures sensitivity, response time and regeneration rate depend on the synthesis method, the dopant and the mole ratio. The ageing effect after 8 months under ambient conditions and the mechanism of interaction between the polyaniline nanostructures and ammonia molecules are also presented.     

Green synthesis of ethyl oxalate benzylidinyl hydrazides

Acylhydrazone compounds play an important role in medicine, materials and other fields. Herein we report the synthesis of ethyl oxalate benzylidinyl hydrazides by the reaction of benzaldehyde derivatives and ethyl oxalate hydrazide under catalyst-free conditions in H₂O near room temperature. This green synthesis method has the advantages of mild reaction conditions, fast reaction rate, non-catalytic, good yield and easy isolation. These synthesized ethyl oxalate benzylidinyl hydrazides can be used as Schiff base metal complexes of small molecule ligands.     

Chelation-mediated aqueous synthesis of metal oxyhydroxide and oxide nanostructures: combination of ligand-controlled oxidation and ligand-cooperative morphogenesis

We have synthesized nanostructures of iron and cobalt oxyhydroxides and manganese oxides in aqueous solution containing a chelating agent. Nanosheets of FeOOH and NaxMnO2 and nanoflakes of CoOOH were generated from the corresponding divalent metal salts and ethylenediaminetetraacetate (EDTA) by one-pot synthesis under ambient conditions. The chelating agent fulfilled multiple roles in the reaction process and morphogenesis leading to two-dimensional nanostructures. Coordination to the divalent metal ions inhibited rapid precipitation of metal hydroxides and mediated oxidation to tri- and tetravalent species by dissolved oxygen. Along with the deposition, the two-dimensional and single-crystal nanostructures were also associated with interactions of the chelating agent. Therefore, this approach can be regarded as a combination of ligand-controlled oxidation and ligand-cooperative morphogenesis. Parallel control of the reaction and the morphology was achieved by a simple approach. The model cases suggest that tailoring chelation can facilitate the design of other metal oxide nanomaterials.     

Generation of carbon nanostructures with diverse morphologies by the catalytic aerosol-assisted vapor-phase synthesis method

The Fe catalyst-supported aerosol-assisted synthesis method was used to prepare carbon products of diverse morphologies from toluene. Aerosol mist generation was accomplished with an ultrasonic device. An open-ended quartz boat for powder collection was placed in the maximum temperature zone of the tube reactor (850 °C or 1000 °C). The morphology of the products was studied by SEM and TEM microscopy. Structural characterization was provided by powder XRD, whereas Raman spectroscopy was used to determine the structural quality/homogeneity of the products. The hydrogen gas sorption capacity of the product prepared at 850 °C was relatively high despite its rather moderate BET specific surface area.     

Formation of polyaniline/Pt nanoparticle composite films and their electrocatalytic properties

Polyaniline (PANI) thin films modified with platinum nanoparticles have been prepared by several methods, characterised and assessed in terms of electrocatalytic properties. These composite materials have been prepared by the in situ reduction of a platinum salt (K₂PtCl₄) by PANI, in a variety of solvents, resulting in the formation of platinum nanoparticles and clusters of different sizes. The further deposition of platinum clusters at spin cast thin films of PANI/Pt composites from a neutral aqueous solution of K₂PtCl₄ has also been demonstrated. Thin-film electrodes prepared from these materials have been investigated for their electrocatalytic activity by studying hydrazine oxidation and dichromate reduction. The properties of the composite materials have been determined using UV–visible spectroscopy, atomic force microscopy and transmission electron microscopy. The nature of the material formed is strongly dependent on the solvent used to dissolve PANI, the method of preparation of the PANI/Pt solution and the composition of the spin cast thin film before subsequent deposition of platinum from the aqueous solution of K₂PtCl₄.Dedicated to Professor Dr. Alan Bond on the occasion of his 60th birthday.     

One‐pot dual size‐ and shape selective synthesis of tetrahedral Pt nanoparticles

One‐pot dual size‐ and shape‐selective synthesis of tetrahedral Pt nanoparticles is achieved using the pre‐prepared Pt nanoparticles as the ‘external seeds’, and controlling the slow diffusional growth under hydrogen reduction in the presence of PVP as the capping agent. Copyright © 2006 John Wiley & Sons, Ltd.     

Controlled synthesis of dendritic ruthenium nanostructures under microwave irradiation and their catalytic properties for p-chloronitrobenzene hydrogenation

Transition Metal Chemistry - In this study, the shape-controlled synthesis of ruthenium (Ru) nanostructures was examined using microwave irradiation. Dendritic Ru nanostructures, with an average...     

Green synthesis of polyimides and their CNT based nanohybrid shish-kebabs through reaction-induced crystallization of nylon-salt-type monomers in glycerol

A green approach to the synthesis and morphological control of high performance polyimides and their nanohybrid shish-kebabs in glycerol through reaction-induced crystallization of nylon-salt-type monomers was reported. Crystalline polyimide nanoplates can be observed by direct polycondensation of pyromellitic acid with various kinds of aliphatic or aromatic diamines. With the existence of carbon nanotuhes, the polyimides can be successfully decorated on the surface of CNTs through a reaction-induced hetero-epitaxial crystallization process, and resulted in novel polyimide/CNT nanohybrid shish-kebabs （NHSKs） structures. The morphologies of the NHSKs can be fine-tuned through changing the concentration of monomers or the reaction temperature, especially through the introduction of dynamic imine chemistry, the formation process of NHSKs can be attributed to a soft epitaxy mechanism. Thus a green approach for the synthesis of high performance polyimides and their CNT based nanohybrid structures was explored, which should be of great value for their applications in high performance reinforced nanocomposites.     

Novel thiosemicarbazone derivatives containing benzimidazole moiety: Green synthesis and anti-malarial activity

A series of (E)-2-[5-chloro-1-(1H-benzo[d]imidazol-2-yl)ethylidene] N-(substituted) hydrazine carbothioamide (7a–7t) and (E)-2-[1-(1H-benzo[d]imidazol-2-yl)ethylidene] N-(substituted) hydrazine carbothioamide (8a–8t) were prepared via the synthesis of 1-(substituted-1H-benzimidazol-2-yl) ethanol (3a–3b) which was synthesized by the condensation of substituted o-phenylenediamine (2a–2b) with dl-lactic acid (1) followed by oxidation with sodium hypochlorite in mild acidic condition to form the corresponding ketones 4a–4b. Final compounds were formed by condensation of 4a–4b with different thiosemicarbazides 6a–6t. A total of 40 compounds were synthesized and characterized by FT-IR, ¹H NMR, ¹³C NMR, Mass spectral technique and elemental analysis, in addition they were evaluated for anti-malarial properties. Among the compounds tested 7o, 7p, 7q, 7r, 7s, 8e and 8h exhibited good antimalarial activity in vitro.     

Preparation of Surfactant-Free Pt and PtRu Nanoparticles with High Activity for Methanol Oxidation

A simple and green approach to synthesize highly active electro-catalysts for methanol oxi- dation reaction （MOR） without using any organic agents is described. Pt nanoparticles are directly deposited on the pre-cleaned and pre-oxidized multiwall carbon nanotubes （MWC- NTs） from Pt salt by using CO as the reductant. MOR activity has been characterized by both cyclic voltammetry and chronoamperometry, the current density and mass specific current at the peak potential （ca. 0.9 V vs. RHE） reaches 11.6 mA/cm^2 and 860 mA/mgpt, respectively. After electro-deposition of Ru onto the Pt/MWCNTs surface, the catalysts show steady state mass specific current of 20 and 80 mA/mgpt at 0.5 and 0.6 V, respectively.     

Green synthesis of platinum nanoparticles by Nymphaea tetragona flower extract and their skin lightening,antiaging effects

Platinum nanoparticles (PtNPs) were green synthesized by using chloroplatinic acid (H₂PtCl₆) as raw material and Nymphaea tetragona (N. tetragona) flower extract as the capping and reducing agents to improve skin health. Size-tunable PtNPs were obtained by volume ratios of the initial H₂PtCl₆/N. tetragona of 1:1 and 1:4, in which PtNPs prepared by the ratio of 1:1 and 1:4 was defined as L1-PtNPs and L4-PtNPs. Their characterizations were investigated by UV–visible spectroscopy, TEM, XRD and FTIR spectroscopy. TEM image analysis showed the particles were well dispersed with the average particle diameters of L1 and L4-PtNPs were 4.04 ± 1.31 nm and 2.01 ± 0.80 nm, respectively. The synthesized PtNPs showed effective antioxidant property and anti-tyrosinase activity in vitro. And further experiments exclaimed that PtNPs can significantly inhibit tyrosinase activity and UVB-induced melanin biosynthesis in A375 cells. This study also revealed PtNPs can promote collagen I biosynthesis in HFF-1 cells by activating the TGF-β/Smad pathway. This research showed the potential efficacy of PtNPs in the skin field and provided evidence for people to consider applying PtNPs to skin protection.     

氧气在不同粒径Pt/C催化剂上的电催化还原

在甲醇溶剂中,利用SnCl2作为还原剂,通过控制反应条件制备了带有不同粒径Pt粒子Pt/C催化剂。X-射线衍射和透射电镜的研究表明获得的Pt/C催化剂中Pt粒子具有高度的均一性和良好的分散度。电化学研究显示,对于氧气的电催化还原,Pt/C催化剂存在着明显的粒径效应。当Pt粒子粒径为3.2 nm时,Pt/C催化剂对氧气的电催化还原的质量比活性最佳。Pt/C催化剂对氧气的粒径效应可能与其表面含氧基团含量、Pt粒子的比表面积及其晶面结构相关。