PSSS‐controlled synthesis of CaCO3 superstructures

Complex CaCO₃ superstructure can be easily synthesized by using poly (sodium 4‐styrenesulfonate) (PSSS) as a structure directing agent to direct the controlled precipitation of calcium carbonate from aqueous solution. The products were characterized by scanning electron microscopy (SEM), and powder X‐ray diffraction (XRD) analysis. The results revealed that the morphology of the products changed significantly with the increasing of the concentration of PSSS in solution, from rhombohedral particles to plate‐packed aggregates to spheres with smooth surface, to sponge‐like spheres and finally to complex spherical superstructure consisted of plate‐like sub‐units. We hypothesize that the observed sequential changes in morphology of CaCO₃ particles with added PSSS concentration may be due to the influence of PSSS on nucleation, growth and aggregation of CaCO₃ crystals. The formation mechanisms of CaCO₃ crystals with different morphologies were discussed. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Controlled synthesis of barium chromate microcrystals

Barium chromate (BaCrO₄) microcrystals with various morphologies such as shuttle‐like, x‐shaped, ellipsoid, leaf‐like crystals were synthesized from aqueous solutions using poly (sodium 4‐styrenesulfonate) (PSS) as template agent at room temperature. The characterization results show that pH values and concentrations of reactants and PSS are important parameters in the morphology and size evolution of BaCrO₄. The possible formation mechanism of BaCrO₄ crystals with different morphologies was proposed. PSS complexes Ba²⁺ first, then affects the nucleation and crystallization process by interacting with the plane face of crystal, which finally results in various morphologies and sizes of crystals. In addition, the possible mechanism of photoluminescence (PL) spectra was also proposed.     

Morphology‐controlled CaMoO4 nanorods via a facile microwave‐assisted EDTA chelating agent process

This work reports on the shape‐controlled synthesis of CaMoO₄ nanorods via a high‐efficient microwave irradiation‐assisted chelating agent method. The phase and microstructure of these materials were systematically characterized by X‐ray diffraction and field‐emission scanning electron microscopy. It is noteworthy that EDTA plays pivotal roles as the complexing and capping agent in the oriented growth of uniform CaMoO₄ nanorods. The synthetic process gives the guidance to understand the morphological evolution of CaMoO₄ microstructures in microwave system, and provides a facile and designed strategy to fabricate functional one dimensional metallic molybdates.     

Solvothermal synthesis of mesoporous slabstone‐like TiO2 and its photodegradation preference in a methyl orange‐rhodamine B mixture solution

Mesoporous slabstone‐like anatase TiO₂ micro‐nanometer composite structure has been successfully synthesized by a facile solvothermal method at 180 °C using polyethylene glycol (PEG) as a structure‐directing agent, followed by calcination at 400 °C for 2 h. The crystal structure and morphology of the product were characterized by XRD, SEM, TEM and HRTEM. Its BET specific surface area was obtained from N₂ adsorption‐desorption isotherm measurement. Rhodamine B (RB) aqueous solution was used to evaluate the photocatalytic activity of the as‐prepared TiO₂ under simulated sunlight irradiation and compared with that of commercial TiO₂ (P25). A RB and methyl orange (MO) coexisting solution was chosen to investigate the photodegradation preference of the slabstone‐like TiO₂ on these two dyes. The results show that the photocatalytic activity of the as‐prepared TiO₂ is much higher than that of P25, and MO is the preferential degradation species in the MO‐RB mixture solution.     

Synthesis of flower‐like zinc oxide and polyaniline with worm‐like morphology and their applications in hybrid solar cells

ZnO with a “flower‐like” morphology was synthesized using a simple microwave assisted hydrothermal method and used as an acceptor material in hybrid solar cells. X‐Ray diffraction and Raman Spectroscopy confirmed the formation of a highly crystalline wurtzite ZnO structure. A highly crystalline and conductive polyaniline with “worm‐like” morphology was synthesized by chemical polymerization of aniline using KH(IO₃)₂ as an oxidant and was used as a donor material for solar cells. The morphology was probed by using scanning and transmission electron microscopy. Polyaniline with worm‐like morphology had a diameter of 160 nm and about 2 µm long. Solar cell device fabricated from PANI/ZnO active bilayer demonstrated a fill factor of about 22.8%. Upon blending PANI with ZnO the fill factor was improved to 25.6% and efficiency by almost 100 fold when PANI:ZnO 1:1 composite was used as an bulk heterogeneous active layer. The fill factor was further improved to 26.4% when device architecture was changed to diffused bilayer. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Influence of citric acid on calcium sulfate dihydrate crystallization in aqueous media

The crystallization of Calcium sulfate dihydrate produced by the reaction between pure Ca(OH)₂ suspension and H₂SO₄ solution was investigated at different pH values, temperatures and citric acid concentrations. Crystal size distributions, filtration rates and zeta potentials of gypsum were determined as a function of citric acid concentrations at pH 3.5 and 65°C. The influence of citric acid on the morphology of gypsum was also investigated and discussed. The average particle size of gypsum was reached to maximum in the presence of approximately 2500 ppm citric acid concentration, where the minimum cake resistance and maximum filtration rate were obtained. In the presence of citric acid, various crystal morphologies such as tabular, plate‐like, double‐taper leaf‐like and flower‐like, etc., were obtained. The change of morphology is related to the preferential adsorption of citric acid on different crystallographic faces. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Additive‐free solvothermal synthesis of peanut‐like BiVO4 powders with enhanced photocatalysis activity

Monoclinic peanut‐like BiVO₄ products have been successfully synthesized by a solvothermal method. The volume of CH₃COOH and the concentration of NH₃·H₂O were found to play important roles in the formation of this morphology. The optimal condition for preparation of highly active peanut‐like BiVO₄ samples are the volume of CH₃COOH, which was 5 ml, and the concentration of NH₃·H₂O, which was 2 mol/L. The as‐prepared samples were characterized by XRD, SEM, TEM, DRS, BET, and their photocatalytic activity was evaluated by photocatalytic decolorization of a Rhodamine B (RhB) aqueous solution under visible‐light irradiation. The results demonstrated that BiVO₄ with peanut‐like morphology was better than that of other BiVO₄ samples for photodegradation of RhB.     

EDTA‐assisted synthesis of rose‐like ZnO architectures

Rose‐like ZnO nanostructures were prepared by a low‐temperature solution route with assistance of ethylenediaminetetraacetic acid disodium (EDTA‐2Na). The morphology of ZnO nanostructures was found to change from nanowire arrays to rose‐ and tower‐like architectures with increasing the molar ratio of EDTA‐2Na/Zn²⁺. Also, the shape evolution of ZnO nanostructures with time was observed from flat nanosheets to wrinkled nanosheets and to rose‐like nanostructures. EDTA‐2Na as a strong complexing agent was found to play a key role in the shape evolution. Photoluminescence spectra show that the rose‐like ZnO architectures have more defects than the nanowire arrays. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Solvothermal synthesis and good electrochemical property of pinetree like Bi2S3

Hierarchical pinetree like Bi₂S₃ was synthesized through a facile solvothermal route in the mixture of deionized water and tetrahydrofuran. The phase composition, morphology, and structure of the as‐prepared Bi₂S₃ products were characterized by using various techniques including X‐ray diffraction (XRD), field emission scanning electron microscopy (FESEM), and transmission electron microscopy (TEM). It was found that the pinetree like Bi₂S₃ structures were composed of numerous assembled nanosheets, which had uniform morphology with the mean width and length of about 110 nm and 15 μm, respectively. Furthermore, the electrochemical property of the obtained pinetree like Bi₂S₃ was investigated. The pinetree like Bi₂S₃ presented both the high electrochemical hydrogen storage and electrochemical Li intercalation performance.     

Low temperature synthesis of spindle‐like ZnO nanostructures under microwave irradiation

A simple and general microwave route is developed to synthesize nanostructured ZnO using Zn(acac)₂·H₂O (acac = acetylacetonate) as a single source precursor. The reaction time has a great influence on the morphology of the ZnO nanostructures and an interesting spindle‐like nanostructure is obtained. The microstructure and morphology of the synthesized materials are investigated by X‐ray diffraction (XRD), scanning electron microscopy (SEM), field‐emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), high‐resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED). It is found that all of them with hexagonal wurtzite phase are of single crystalline structure in nature. Ultraviolet–visible (UV‐vis) absorption spectra of these ZnO nanostructures are investigated and a possible formation mechanism for the spindle‐like ZnO nanostructures is also proposed.     

Graphene oxide used as a surfactant to induce the flower‐like ZnO microstructures: growth mechanism and enhanced photocatalytic properties

In this paper, graphene oxide (GO) was used as a temple to induce the formation of flower‐like ZnO microparticals compared with surfactants, such as cetyltrimethylammonium bromide (CTAB) and dodecyl dimethyl betaine (BS‐12). The zinc hydroxide carbonate ((Zn₄(CO₃)(OH)₆,ZHC)) was produced by a hydrothermal reaction. The flower‐like ZnO microparticals were gained by calcining ZHC. In the GO medium, the microparticals were assembled by numerous porous nanosheets from one point (initial nucleus) to flower‐like microparticals finally. The nanosheets of graphene oxide and functional groups were likely to contribute to the formation of the precursor, and some nanosheets were retained in the complex. The growth mechanism of ZHC was also proposed in this paper. The photocatalytic activity of the flower‐like ZnO microparticals was evaluated by photo degradation reaction of rhodamine B (RhB). The peony‐like porous ZnO/rGO compounds showed high photocatalytic activity and better than ZnO microparticals formed in the CTAB and BS‐12. These results indicated that GO could be widely used as a surfactant to induce composite materials with special morphology and photoelectric properties, etc.     

synthesis of high‐quality crystalline α‐MoO3 nanobelts

High‐quality crystalline MoO₃ nanobelts were successfully fabricated with a facile hydrothermal route by using common and inexpensive NaCl as a capping agent. The products are thoroughly characterized by the combination of different techniques. The results indicate that as‐prepared MoO₃ nanobelts have an orthorhombic crystal structure (α‐MoO₃) with growth preferential in the [001] direction, the size of the obtained MoO₃ nanobelts ranges from 200 nm to 300 nm in width and micrometers in length. The effects of the amount of NaCl on the morphology and size of the resultant MoO₃ were also investigated, it is clearly shown that the presence of appropriate amount of NaCl plays a crucial role in controlling the size and morphology of the obtained MoO₃. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Surface‐morphology evolution of ZnO nanostructures grown by hydrothermal method

Surface‐morphology evolution of ZnO nanocrystals has been observed by the hydrothermal process. The effects of stirring time and ammonia content on the morphology evolution have been discussed, respectively. Extension of stirring time of the precursor results in morphology transformation from star‐like to wire‐like ZnO nanocrystals. ZnO nuclei aggregation and uniform Zn(OH)₂ precipitation can readily explain these two morphologies, respectively. By increasing the ammonia content in the solution, the morphology of ZnO crystals is transformed from an irregular shape to hexagon sheets to nanorods, and the side length of ZnO crystals is decreased accordingly. Hollow structures are realized at the subsequent solution aging process. Variation of zinc ammonic complex and minimum surface energy can well explain the morphology evolution of ZnO nanostructures.     

Ionic liquid‐assisted hydrothermal synthesis of γ‐Al2O3hierarchical nanostructures

The boehmite (Al₂O₃·H₂O) hierarchical nanostructure with spindle‐like morphology has been successfully synthesized via ionic liquid‐assisted hydrothermal synthetic method under mild condition using an ionic liquid 1‐butyl‐3‐dimethylimidazolium bromide ([Bmim][Br]) as a template. The proposed formation mechanism has been investigated and the hydrogen bond‐co‐π–π stack mechanism is used to be responsible for the present formation of the precursor hierarchical nanostructure. The γ‐Al₂O₃ hierarchical nanostructure was obtained by calcining the as‐synthesized precursor at 500 °C for 2 h, preserving the same morphology. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Preparation of shuttle‐like Sb2S3 nanorod‐bundles via a solvothermal approach under alkaline condition

Uniform shuttle‐like Sb₂S₃ nanorod‐bundles were synthesized via a polyvinylpyrrolidone (PVP) assisted solvothermal approach under alkaline condition, using antimony chloride (SbCl₃) and thiourea (CH₄N₂S, Tu) as the starting materials in ethanol. The phase structure, composition and morphology of the product were characterized by means of X‐ray diffraction (XRD), energy dispersive X‐ray spectrometry (EDS), transmission electron microscopy (TEM), and high‐resolution transmission electron microscopy (HRTEM). XRD and EDS results confirm that the synthesized Sb₂S₃ nanorod‐bundles have an orthorhombic structure and an atomic ratio of 3:2 for S:Sb. TEM and HRTEM results show that the shuttle‐like Sb₂S₃ bundles are composed of nanorods with a size distribution of 20‐40 nm and growing along c‐axis. Furthermore, experiments under different reaction conditions were carried out and the mechanism for the growth of nanorod‐bundles was discussed (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Capsule‐like α‐Fe2O3 nanoparticles: Synthesis,characterization, and growth mechanism

Uniform capsule‐like α‐Fe₂O₃ particles were synthesized via a simple hydrothermal method, employing FeCl₃ and CH₃COONa as the precursors and sodium dodecyl sulfate (SDS) as soft template. X‐ray powder diffraction (XRD), field emission scanning electron microscopy (FE‐SEM), transmission electron microscopy (TEM), and high‐resolution transmission electron microscopy were used to characterize the structure of synthesized products. Some factors influencing the formation of capsule‐like α‐Fe₂O₃ particles were systematically investigated, including different kinds of surfactants, the concentration of SDS, and reaction times. The investigation on the evolution formation reveals that SDS was critical to control the morphology of final products, and a possible five‐step growth mechanism was presented by tracking the structures of the products at different reaction stages.     

Surfactant‐assisted synthesis of novel star‐like PbWO4 hierarchical architectures

Large‐scale star‐like PbWO₄ hierarchical architectures were controllably synthesized by a facile surfactant‐assisted technology under mild conditions in the presence of a mixed solvent of ethylene glycol and water. The morphology, structure, and phase composition of PbWO₄ architectures were characterized by X‐ray diffraction (XRD), field emission scanning electron microscopy (FE‐SEM), field emission transmission electron microscopy (FE‐TEM), and nitrogen adsorption‐desorption isotherms. The possible formation mechanism of the star‐like PbWO₄ architectures (initial nucleating stage and a subsequent self‐assembly stage) was proposed based on the observations from a time‐dependent morphology evolution process, which may pave the way to shape‐controlled synthesis of inorganic nanocrystals with the complex structures. This route provides a facile strategy to fabricate complex hierarchical PbWO₄ structures. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and characterization of semiconductor metal sulfide nanocrystals using microemulsion technique

The semiconductor nanocrystals ZnS, PbS, CdS and CuS were synthesized via microemulsion technique involving metal acetate, reducing agent (Na₂S) and Triton X‐100 as surfactant. Nanocrystals were characterized by X‐ray diffraction (XRD), transmission electron microscopy (TEM) and dynamic light scattering (DLS). The average size of ZnS, PbS, CdS and CuS nanocrystals were found to be 5.6 nm, 13.3 nm, 11.4 nm and 6.2 nm, respectively. Different parameters like surfactant (Triton X‐100) concentration, water‐to‐surfactant ratio (ω), precursor concentration [zinc acetate, (Zn(AC)₂], reducing agent concentration [sodium sulphide, (Na₂S)] were optimized to synthesize ZnS quantum dots.     

Solvothermal synthesis and growth mechanism of asymmetric ZnO hierarchical structures in diethylene glycol with ammonia solution

Several novel asymmetric ZnO hierarchical structures were synthesized in diethylene glycol (DEG) with different amount of ammonia solution via solvothermal process. The submicron‐rods or nanorods as the building units are distributed on the two sides in an asymmetric manner, resulting in formation of the shiitake‐like or bouquet‐like morphology. A possible formation mechanism was proposed on the basis of the experimental result. The consumption of the precursor could lead to a two‐step nucleation and growth process. The relative content of the [Zn(OH)₄]²⁻ and the [Zn(NH₃)₄]²⁺ precursors varies with the amount of ammonia solution, which affect the size and morphology of the asymmetric structures. The [Zn(OH)₄]²⁻ complex and the [Zn(NH₃)₄]²⁺ complex are absorbed on the positive (0001)‐Zn polar surface and the negative (000–1)‐O polar surface respectively, which lead to the alteration of growth rate of these polar surfaces.     

Preparation of CuO mesocrystals via antlerite intermediate for photocatalytic applications

CuO mesocrystals were synthesized by thermal decomposition of antlerite (Cu₃(OH)₄SO₄) formed as an intermediate by the reaction between CuSO₄.5H₂O and urea under specific experimental conditions. Antlerite possessing spindles of sea urchin‐like morphology was obtained via controlled hydrolysis process using ethylene glycol as a co‐solvent. Antlerite and CuO mesocrystals were characterized by X‐ray diffraction (XRD), fourier transform‐infrared spectrum (FT‐IR), thermo gravimetric analysis (TGA), field emission scanning electron microscopy (FESEM) and energy dispersive spectroscopy (EDS). A probable mechanism for formation of such morphologies has been proposed. The photocatalytic and optical properties of CuO mesocrystals were also evaluated.