•A new anode LiFeP was investigated for lithium ion batteries.•The layered structure of LiFeP was relatively stable during cycling.•A discharge capacity of 507 mA h g−1 at 300 mA g−1 after 300 cycles was obtained.•The reason for the increase in capacity of LiFeP was studied.Transition metal phosphides are promising anode materials for lithium ion batteries because of their abundant natural resources and high theoretical capacities. In this study, the electrochemical properties of LiFeP as an anode material for lithium ion battery were investigated for the first time. LiFeP powders were successfully synthesized by a conventional two-step solid-state reaction method. The results of X-ray powder diffraction and selected area electron diffraction revealed that the layered plate-like LiFeP was stacked by the (001) crystal plane. As an electrode material, LiFeP delivered a superior reversible capacity of 507 mA h g−1 at a high current density of 300 mA g−1 after 300 cycles and excellent rate performance. After cycling, the layered structure can be well maintained, which would be greatly beneficial to the electrochemical performance of LiFeP. The reason for the increase in capacity was also investigated and can be attributed to the high number of conversion reactions of LiFeP and the generation of elemental P during cycling.Download high-res image (264KB)Download full-size image

•3R-NaxNbS2 was synthesized through a facile method for the first time.•Homogeneous samples of 3R-NaxNbS2 were obtained by ethanol etching.•The electrical and magnetic properties were investigated•A minimum resistivity was observed for all the investigated samples.Here we report the facile synthesis of alkali metal intercalation compounds AxNbS2 (A = Li, Na) through the reaction of bulk 3R phase of NbS2 with organometallic compounds in solution. Especially, the Na insertion compound of various compositions was obtained as a new polytype of AxNbS2 compared with the 2H phase reported previously. Upon intercalation the structure of the host was preserved, which was confirmed by XRD and HRTEM analysis. The interlayer distances for Li0.44NbS2 and Na0.87NbS2 were expanded by 0.187 Å and 0.938 Å as a result of Li and Na intercalation, respectively. The electrical transport properties were studied in the temperature range 4–298 K, exhibiting metallic conductivity and slight variation in the resistivity value in general. Interestingly, a minimum resistivity which was ascribed to the localized electrons in the crystal lattice emerged for all the investigated samples.

The d-glucopyranose rings modified H2CaTa2O7 was further treated with 2-butanone solution of LiClO4. Li+ ion deposited on the interlayer of H2CaTa2O7, and the interlayer distance of the samples changed into 19.243(1) Å. The AC impedance measurements on the as-prepared samples exhibit improved ionic conductivity compared with original Li2CaTa2O7 sample.The d-glucopyranose rings modified H2CaTa2O7 was further treated with 2-butanone solution of LiClO4, the as-prepared sample exhibiting ionic conductivity.Figure optionsDownload full-size imageDownload as PowerPoint slide

•Fluorination of La2−xSrxCuO4 (x = 0, 0.15, 0.3) by ZnF2 with few byproducts.•Less of impurities are benefit to research its structure and properties.•Suffering a phase transformation and unit cell expansion after fluorination.•Determining chemical formula and fluorine ions occupation of fluorinated product.Here we report using the transition metal difluoride ZnF2 to fluorinate K2NiF4-type cuprates La2−xSrxCuO4 (x = 0, 1.5, 0.3). Unlike other fluorinating agents, the technique is nontoxic, easy to handle and the byproduct ZnO can be removed. After fluorination, the fluorinated product of La2CuO4 suffers a phase transformation and unit cell expansion. While La1.85Sr0.15CuO4 and La1.7Sr0.3CuO4 indicate no change in structure after fluorination, their space groups still are I/4mmm, however, their lattices become larger, too. We emphasis the structural characterizations for fluorinated product of La1.7Sr0.3CuO4 by high-resolution transmission electron microscopy (HRTEM) images and electron diffraction (ED) patterns. Moreover, we determine the chemical formula to be La1.54Sr0.46CuO3.1F0.9 and the fluorine ions are prone to be located in the apical sites of the Cu(O, F)6 octahedron in the structure of post-treated fluorinated product of La1.7Sr0.3CuO4. Magnetization investigations demonstrate that partial replacement of the lanthanum by strontium changes the magnetism of post-treated fluorinated products of La2−xSrxCuO4 (x = 0, 0.15, 0.3) and they exhibit a paramagnetic behavior.

D-Glucopyranose rings have been successfully coordinated onto the interlayer surface of a Ruddlesden–Popper-type layered perovskite, H2CaTa2O7, by a reaction with the precursor of n-decoxyl derivative of H2CaTa2O7. The interlayer distance of D-glucopyranose derivative of H2CaTa2O7 was decreased to 19.135(5) Å compared to 35.026(0) Å for n-decoxyl derivative of H2CaTa2O7. IR and solid-state 13C CP/MAS NMR spectra indicated that the oxyalkyl chains of the precursor were replaced by glucopyranose rings. To extend inorganic–organic hybrids, the H2CaTa2O7 modified was further treated with [Ag(NH3)2]+ solution. Ag nanoparticles are deposited on the interlayer of H2CaTa2O7, and the interlayer distance of the samples is changed into 10.816(6) Å. The as-prepared nanohybrids (Ag/H2CaTa2O7) exhibit an excellent catalytic property for the catalytic reduction of both rhodamine B (RhB) and 4-nitrophenol (4-NP) by NaBH4 aqueous solution; therefore, it is a practical and efficient nanocatalyst.

CdSnO3 materials have been extensively studied as gas-sensing materials. However, there are few reports on the synthesis and use of porous CdSnO3 nanostructures for energy storage. Herein, we report highly porous CdSnO3 nanoparticles prepared using citric acid with sizes in the range of ∼7.8 nm to 28.7 nm and the application of these nanoparticles as an anode material for rechargeable Li-ion batteries (LIBs). Electrochemical measurements showed that the highly porous CdSnO3 nanoparticles delivered a high reversible capacity of ∼515 mA h g−1 for up to 40 cycles at a current rate of 70 mA g−1. Even at a high rate of 150 mA g−1, the porous CdSnO3 could still deliver a capacity of 506 mA h g−1. It is observed that the electrochemical performance of the highly porous CdSnO3 nanoparticles is much better than that (∼370 mA h g−1 for up to 40 cycles) of a counterpart obtained without citric acid, which also demonstrates the capacity enhancement and high rate capacity.

N-alkyl chains have been successfully grafted into the interlayer space of a Ruddlesden–Popper-type double-layered peroviskite, H2CaTa2O7, via a hydrolysis–esterification process. During the chemical graft process, the parent layered structure is well preserved with magnifying the tailored c lattice parameter. IR and solid-state 13C CP/MAS NMR spectra indicated that oxyalkyl chains were successfully introduced. Thermogravimetric curves of the products exhibit the amount of n-alkoxyl groups per perovskite unit [CaTa2O7] is approximated to 1. A linear relationship with a slope of 0.478 nm per carbon atom is observed between the c lattice parameter and the number of carbon atoms in the n-alkyl chains, which illustrates that the n-alkyl chains form bilayers with a tilt angle of 70°. The photocatalytic activities of these products are also discussed. The 1-octadecanol derivative of H2CaTa2O7 is found to serve as an excellent catalyst for the catalytic reduction of rhodamine B (RhB) and methyl orange (MO), which is set as a novel example of an application of this tailored n-propoxy derivative of H2CaTa2O7.

In this work, AgInS2 hierarchical flowerlike nanoarchitectures, which are composed of ultrathin nanowires, were synthesized by thermolysis of a mixed solution of AgNO3, InCl3·4H2O and n-dodecanethiol at elevated temperature. The average diameter and length of the nanowires composing the nanoarchitectures can reach 5 nm and ∼300 nm, respectively. We investigated the growth process of the nanoarchitectures and the effects of reaction parameters by XRD, SEM and TEM. In particular, the use of InCl3·4H2O played a decisive role in the synthesis of the nanoarchitectures. Moreover, it was found that polyhedra formed in the initial reaction time, and then the nanowires grew on the facets of these polyhedra, which resulted in the nanoarchitectures. The reaction temperature and the concentration of metal salts could influence the size of the nanowires.

CuInS2 nanocrystals were synthesized by one-pot thermolysis of a mixture solution of metal chlorides, 1-dodecanethiol (DT) and oleic acid in noncoordinating solvent 1-octadecene. Interestingly, in this synthesis, different structures and shapes were obtained by simply varying the dosage of DT. At a low dosage of DT, wurtzite nanoplates formed in the initial reaction stage and then they further grew to nanoplates with wurtzite–zincblende polytypism as the reaction proceeded. On the contrary, a high dosage of DT produced zincblende nanoparticles. The formation processes of nanoplates and nanoparticles were studied and a growth mechanism was proposed. Our research will aid in solution-synthesis of ternary chalcogenide nanocrystals and the development of their optoelectronic devices.

HLaNb2O7 nanosheets and Ag nanoparticles/clusters were assembled to produce a novel 3D metal/semiconductor hybrid material (Ag/HLaNb2O7) by direct reaction of the undried D-glucopyranose derivative of HLaNb2O7 with [Ag(NH3)2]+ ion aqueous solution. The as-prepared samples were characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, UV-visible diffusive reflectance spectroscopy and nitrogen adsorption–desorption isotherms. The results showed that the simple self-assembly of HLaNb2O7 nanosheets and Ag nanoparticles/clusters formed a mesoporous material with a broad pore size distribution in the range of about 10–35 nm. The mesopores derived from the interspaces between HLaNb2O7 nanosheets and were attributed to Ag nanoparticles, rather than Ag clusters in the interlayer space of HLaNb2O7. The catalytic activity experiments revealed that the product (Ag/HLaNb2O7) was an excellent catalyst for the catalytic reduction of 4-nitrophenol (4-NP) and rhodamine B (RhB) by NaBH4 aqueous solution.

In this work, nanocrystalline-assembled bundle-like CuO structures were successfully synthesized in large-quantity by a friendly, facile two-step process. The bundle-like CuO particles are produced by thermolysis of bundle-like Cu(OH)2 precursors, which exhibit excellent high specific capacity, high stability, and especially high rate performance for anode materials in lithium-ion batteries, superior to that of most reported CuO-based anodes. The assembled structure of CuO endows it with high rate capacities of 666 mAh g−1, 609 mAh g−1, and 499 mAh g−1 at a current rate of 0.3 C, 1 C and 2 C after 50 cycles, respectively. Even at a high rate of 6 C, the bundle-like CuO can still deliver a capacity of 361 mAh g−1. It is observed that the electrochemical performance of the nanocrystalline-assembled bundle-like CuO is much better than that of CuO nanoparticles obtained by destroying the assembled bundle-like CuO through grinding. XRD analysis of both the electrodes after ending the discharge/charge proved that during the discharge/charge process, the conversion reactions occurring in the assembled structures have better reversibility, leading to the high rate capacity and cycling performances. The better reversibility originates from the better contact area for CuO/electrolyte, enhancing many sites to the access of Li+ in the electrolyte Li+. In addition, the assembled bundle-like CuO architectures can also relieve the volume variations during the Li+ uptake–release process, which also contributes to the excellent electrochemical performance. The high rate capacity and enhanced cycling stability of the bundle-like CuO structure make it a promising candidate as an anode material for high-performance Li-ion batteries.

Various CuO nanostructures have been well studied as anode materials for lithium ion batteries (LIBs); however, there are few reports on the synthesis of porous CuO nanostructures used for anode materials, especially one-dimensional (1D) porous CuO. In this work, novel 1D highly porous CuO nanorods with tunable porous size were synthesized in large-quantities by a new, friendly, but very simple approach. We found that the pore size could be controlled by adjusting the sintering temperature in the calcination process. With the rising of calcination temperature, the pore size of CuO has been tuned in the range of ∼0.4 nm to 22 nm. The porous CuO materials have been applied as anode materials in LIBs and the effects of porous size on the electrochemical properties were observed. The highly porous CuO nanorods with porous size in the range of ∼6 nm to 22 nm yielded excellent high specific capacity, good cycling stability, and high rate performance, superior to that of most reported CuO nanocomposites. The CuO material delivers a high reversible capacity of 654 mA h g−1 and 93% capacity retention over 200 cycles at a rate of 0.5 C. It also exhibits excellent high rate capacity of 410 mA h g−1 even at 6 C. These results suggest that the facile synthetic method of producing a tunable highly porous CuO nanostructure can realize a long cycle life with high reversible capacity, which is suitable for next-generation high-performance LIBs.

Carbon was successfully intercalated into the interlayer space of the Dion–Jacobson type layered perovskite HLaNb2O7 by pyrolysis of the precursor of a D-glucopyranose derivative of HLaNb2O7. Firstly, the D-glucopyranose derivative of HLaNb2O7 (D-glucopyranose-HLaNb2O7) was prepared by the grafting reaction between the n-decoxyl derivative of HLaNb2O7 and D-glucopyranose. The interlayer distance of D-glucopyranose-HLaNb2O7 was decreased to 15.4 Å, compared to that of 27.6 Å for n-decoxyl-HLaNb2O7. IR and solid-state 13C CP/MAS NMR spectra indicated that oxyalkyl chains were removed and glucopyranose rings were introduced. After pyrolysis of the D-glucopyranose derivative at 300 °C under flowing Ar, a novel intercalation compound of HLaNb2O7 with carbon (carbon-HLaNb2O7) was obtained. XRD pattern and HRTEM image both displayed the interlayer distance of about 12 Å. Raman and solid-state 13C CP/MAS NMR spectra revealed that the intercalated carbon was mainly polycyclic aromatic carbon. The UV-VIS-near-IR spectrum showed that the carbon-HLaNb2O7 appreciably absorbed light at wavelengths below 855 nm and the band gap energy was only about 0.65 eV, which was much smaller than those of HLaNb2O7 and its derivatives, indicating that the intercalation with carbon can effectively modify the band gaps of Dion–Jacobson type layered perovskites.

The synthesis of single-crystalline hollow particles with well-defined non-spherical shapes, especially hollow complex compounds, remains a significant challenge. In this paper, single-crystalline ZnSn(OH)6 (ZHS) hollow cubes were first synthesized by a facile self-templating method at room temperature. On the basis of X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy and transmission electron microscopy, it was found that hollow ZHS cubes were formed by a two-step process, in which solid cubes of ZHS were formed in the first step due to the co-precipitation of Zn(II) and Sn(IV) under basic conditions and then the solid cubes as the self-templates were converted to hollow ones through an alkali-assisted dissolution process. During the process, NaOH solution added in the second step is critical to the formation of ZHS hollow structures. The photocatalytic activity of ZHS hollow cubes for phenol degradation was tested, which showed much higher catalytic activity than that of the solid ZHS cubes. After four trials, the photocatalytic activity of the ZHS hollow cubes exhibits no significant loss.

Monodisperse hollow and core-shell magnetite (Fe3O4) spheres have been prepared by a simple one-pot method based on hydrothermal treatment of FeCl3, citrate, polyacrylamide and urea. The as-prepared samples have been characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, nitrogen adsorption-desorption isotherms, superconducting quantum interference device magnetometer. The results of control experiments reveal that citrate and polyacrylamide are crucial for the formation of spherical product and the well known Ostwald ripening process is responsible for the transformation from solid spheres to hollow and core-shell spheres. The hollow and core-shell magnetite spheres are porous and highly water soluble. They exhibit superparamagnetic properties with relatively high saturation magnetization at room temperature. The superparamagnetic properties, high magnetization, high water solubility, together with the hollow interiors will render them ideal candidates for various biomedical applications.

In this work, a facile route using simple a hydrothermal reaction and sequential calcinations for the selective synthesis of 3D α-Fe2O3 urchinlike nanostructures without employing templates or matrixes is presented. By hydrolyzing FeCl3 in the solution containing different anions (SO42−, Cl−, NO3−, ClO3−, ClO4−, C2O4−, Br−), product with certain morphology can be selectively synthesized. The effect of inorganic anions on the morphologies and sizes of the products was systematically investigated. A probable formation mechanism for the urchinlike nanostructure was proposed. Magnetic hysteresis measurements of the as-obtained products reveal that magnetic properties of products were shape-dependent. The as-obtained α-Fe2O3 nanostructures show photocatalytic activity on the decomposition of RhB upon irradiation by the UV light. The photocatalytic performance can be further enhanced by TiO2 coating.

Monodisperse Cu2WO4(OH)2 round and elliptical hollow spheres have been successfully prepared by a ligand-assisted dissolution process, without any template or surfactant.

A new chemical fluorination method to insert fluorine into Sr2CuO3 and NdSr2Cu2O6−δ under solvothermal conditions is introduced. X-ray powder diffraction and magnetic susceptibility measurements show that the fluorinated Sr2Cu(O, F)4+δ is a superconductor with superconducting transition temperature Tc = 38 K, and the fluorinated NdSr2Cu2(O, F)6+δ displays a structural change from orthorhombic structure to tetragonal structure without superconducting properties. This investigation indicates that it is feasible to insert fluorine into the structures of cuprates by solvothermal fluorination. In addition, the fluorination mechanism and the unique properties of the closed system are discussed.

A facile complex homogeneous precipitation method was successfully employed for the preparation of MnCO3 and Mn(OH)2 crystals using hydrazine hydrate as the complexing agent in a hydrothermal system. The morphology of the products could be simply controlled by changing the reactant, the reaction temperature and the reaction time. X-ray powder diffraction results showed that the as-prepared MnCO3 and Mn(OH)2 products could be indexed to the rhombohedral and hexagonal structure, respectively. The morphologies of the products were investigated by scanning electron microscopy, field-emission scanning electron microscopy, and transmission electron microscopy. It can be seen that the products showed various morphologies such as MnCO3 cocoons, prisms, spindles, anamorphic rhombohedra and Mn(OH)2 quasi-hexagonal nanosheets, dumbbells, nanoflake bundles.

Micropolyhedra, microspheres and hollow microspheres of the cubic KMnF3 were selectively prepared by controllable, hydrothermal method at 120 °C. Manganese acetate and potassium fluoride were employed as the starting materials in the reaction, and variety of polyethylene glycol and dosage of citric acid were demonstrated to be responsible for the shape evolution. The samples were characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectra, UV–vis absorption spectroscopy and photoluminescence spectra. A possible mechanism for the growth of KMnF3 microcrystal was proposed.Micropolyhedra, microspheres and hollow microspheres of the cubic KMnF3 were selectively prepared by controllable, hydrothermal method at 120 °C. The variety of polyethylene glycol and dosage of citric acid were demonstrated to be responsible for the shape evolution. It is interesting that these microstructures can be obtained by just modifying one reaction parameter in the reaction.

A new wurtzite (WZ) structure CuInS2, space group P63mc, a = 3.90652(13) Å, c = 6.42896(23) Å, has been synthesized by a one-step solvothermal method. Analogous with the disordered zinc-blende structure, wurtzite structure is metastable at room temperature and considered as a disordered polymorph of chalcopyrite (CH) structure, where Cu and In atoms randomly occupy the cation sublattice positions. It is believed that the solvent of ethanolamine plays an important role in the synthesis of WZ-CuInS2. The coordination between Cu2+ and −NH2 of ethanolamine molecules favors the nucleation and growth of WZ-CuInS2. Differential scanning calorimeter, together with X-ray diffraction analysis, revealed a phase transition from WZ-CuInS2 to CH-CuInS2 when WZ-CuInS2 was heated to certain temperature. The visible and near-infrared absorption spectra show that the as-prepared nanostructured WZ-CuInS2 has distinct optical properties compared with conventional CH-CuInS2.

Hollow CuInS2 microspheres have been successfully prepared via a simple solution-based route without employing templates and surfactants. Transmission electron microscope (TEM) images clearly show the hollow nature of the as-obtained products. Field emission scanning electron microscopy (FESEM) images reveal that the shells of as-prepared CuInS2 microspheres were constructed by nanoparticles or nanoflakes. The specific surface area and pore-size distribution of the obtained product as determined by gas-sorption measurements show that the CuInS2 hollow microspheres exhibit high Brunauer–Emmett–Teller (BET) surface area and porosity properties. TEM observations of intermediate products at different reaction stages indicate that these hollow CuInS2 microspheres are formed mainly via Ostwald ripening.

A new four-layer Aurivillius phase Bi2SrNa2Nb4O15 has been synthesized by solid-state reaction of Bi2SrNb2O9 and NaNbO3 at 1100 °C. The detailed structure determination of Bi2SrNa2Nb4O15 performed by powder X-ray diffraction (XRD) shows that it crystallizes in the space group I4/mmm [a∼3.9021(1) Å, c∼40.7554(10) Å]. Protonated form of Bi2SrNa2Nb4O15 was obtained by the substitution of bismuth oxide sheets with protons via acid treatment. The conversion into the protonated forms was achieved easily using 6 M HCl at room temperature. Preservation of the structure of the perovskite-like slabs and contraction in the c-axis were confirmed by X-ray analysis. The compositions of the resulting products were determined to be H1.8[Sr0.8Bi0.2Na2Nb4O13] by X-ray fluorescence spectroscopy (XFS) and thermogravimetry.A new four-layer Aurivillius phase Bi2SrNa2Nb4O15 has been successfully synthesized. The powder X-ray diffraction shows that Bi2SrNa2Nb4O15 crystallizes in the space group I4/mmm [a∼3.9021(1) Å, c∼40.7554(10) Å]. Protonated form of Bi2SrNa2Nb4O15 was obtained by the substitution of bismuth oxide sheets with protons via acid treatment. The compositions of the protonated products was determined to be H1.8[Sr0.8Bi0.2Na2Nb4O13] by X-ray fluorescence spectroscopy and thermogravimetry.

A new two-layer Ruddlesden–Popper phase Li2CaTa2O7 has been synthesized for the first time. The detailed structure determination of Li2CaTa2O7 performed by powder X-ray diffraction (XRD) and electron microscopy (ED) shows that it crystallizes in the space group Fmmm [a∼5.5153(1), b∼5.4646(1), c∼18.2375(3)Å]. UV–visible diffuse reflection spectrum of the prepared Li2CaTa2O7 indicates that it had absorption in the UV region. The photocatalytic activity of the Li2CaTa2O7 powders was evaluated by degradation of RhB molecules in water under ultra visible light irradiation. The results showed that Li2CaTa2O7 has high photocatalytic activity at room temperature. Therefore, the preparation and properties studies of Li2CaTa2O7 with a two-layer Ruddlesden–Popper structure suggest potential future applications in photocatalysis.Crystal structure of a two-layer Ruddlesden–Popper phase Li2CaTa2O7A new two-layer Ruddlesden–Popper phase Li2CaTa2O7 has been synthesized for the first time. Li2CaTa2O7 crystallizes in the space group Fmmm determined by powder X-ray and electron diffraction. UV–visible diffuse reflection spectra and the photocatalytic degradation of RhB molecules in water under ultra visible light irradiation show that Li2CaTa2O7 is a potential material in photocatalysis.

In this work, a facile route using simple hydrothermal reaction and sequential calcinations to synthesize 3-dimensional flower-like Y2O3:Eu3+ nanoarchitectures without employing templates or matrix for self-assembly is presented. The flower-like nanostructures are composed of nanosheets with thickness of about 30 nm, which is verified by the field-emission electron microscopy (FESEM). Influencing factors such as the dosage of reactants, the solvent, and pH are systematically investigated. The time-dependent experiments indicate a self-assembly mechanism. This method is also applicable in the preparation of other lanthanide oxides. The PL spectra of the as-synthesized Y2O3:Eu3+ are systematically studied. Both the Eu3+ concentration and the calcinations temperature have great effect on the luminescence intensity of 5D0–7F2 transition. The decay curve of the 5D0 transition shows that the lifetime of the as-obtained Y2O3:Eu3+ is about 2.4 ms.The sample is composed of a large number of uniform flower-like nanostructures. The average size of the as-obtained nanostructure is about 6 μm. A closer inspection further reveals that the flower is made up of many thin petals, the thickness of which is ca. 30 nm.

Uniform α-Fe2O3 nanorods with diameter of about 30 nm and length up to 500 nm were synthesized by a template-free hydrothermal method and a following calcination of the intermediate product in the air at 500 °C for 2 h. By carefully tuning the concentration of the reactants, a series of α-Fe2O3 nanorods with gradient in aspect ratios can be obtained. The effect of the solvent was also evaluated. Based on the experimental facts, the formation mechanism of this one-dimensional structure was proposed. The size-dependent properties of the as-obtained α-Fe2O3 nanorods were investigated. The optical absorption properties of the samples showed that the band gaps of the samples decreased in the sequence in which the size increased. The electrochemical performance of the samples showed that the discharge capacity decreased as the size of the sample increased, which may result from the high surface area and small size. The magnetic hysteresis measurements taken at 5 K showed that the coercivities of the samples were related to the aspect ratios of the samples, which may result from the larger shape anisotropy. However, the temperature-dependent field cooling magnetization showed that there was no Morin transition in the as-prepared samples, which may result from the surface effect.The products are composed of a large number of nanorods. These rods, about 30 nm in diameter and up to 400 nm long, have smooth surfaces along their entire length.

Ultra-long (several millimeters) single-crystalline zigzag tin dioxide nanobelts growing along the [101] crystal direction were prepared by a chemical vapor transport epitaxy (CVTE) method at 850 °C. The product was characterized using X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and an X-ray energy-dispersive spectrometer (EDS). Studies indicate that the zigzag nanobelts are single tetragonal SnO2 crystals with a width of hundreds of nanometers. The optical property was also investigated by the photoluminescence (PL) spectra. The possible formation mechanism of these ultra-long zigzag-like nanobelts was proposed on the basis of experiments.

A facile room-temperature synthesis has been developed to prepare colloidal Mn3O4 and γ-Fe2O3 nanoparticles (5 to 25 nm) by an ultrasonic-assisted method in the absence of any additional nucleation and surfactant. The morphology of the as-prepared samples was observed by transmission electron microscopy. High-resolution transmission electron microscopy observations revealed that the as-synthesized nanoparticles were single crystals. The magnetic properties of the samples were investigated with a superconducting quantum interference device magnetometer. The possible formation process has been proposed.

The precursor manganese carbonate was synthesized via a hydrothermal reduction route. After decomposition of the above precursor, α-Mn2O3 and MnO could be successfully obtained under the atmosphere of air and argon, respectively. The morphology of α-Mn2O3 and MnO was directly determined by that of precursor MnCO3. It is found that the pH is the vital factor affecting the morphology of precursor MnCO3. The products were characterized by X-ray diffraction and scanning electron microscopy.

α-MnSe uniform nanospheres and nanorods were prepared via a simple solvothermal reaction in ethanol amine at 180 °C for 12 h. X-ray powder diffraction (XRD), field-emission scanning electronic microscopy (FE-SEM), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were employed to study the crystal structure and morphologies. The FE-SEM and TEM images showed that the α-MnSe nanospheres had a uniform diameter of about 200 nm and the size of the nanorods was about 50 nm in diameter. The optical properties of the products were also examined by means of UV–Vis absorption, excitation and photoluminescence spectroscopy.

3D flowerlike ZnO nanostructures were synthesized by a simple hydrothermal process. X-ray powder diffraction, scanning electron microscopy and transmission electron microscopy were used to characterize its structure and formation process. The relationship between the experimental conditions and the 3D nanostructures was discussed and the possible growth mechanism was also discussed based on the experimental results.

LaMn2O5 nanorods have been successfully synthesized by oriented attachment assisted growth route at 250 °C for 24 h, which La2O3, HNO3, KMnO4, MnCl2·4H2O and KOH were used as reactants. The products were characterized by XRD, TEM and HRTEM, respectively. The possible growth mechanism for the LaMn2O5 nanorods was discussed.

ZrS3 nanocrystallites have been synthesized via a solvothermal route by the reaction between ZrCl4 and thiourea at relatively low temperature. The product was characterized by X-ray diffraction (XRD), transmission electron microscope, X-ray fluorescence, Raman spectrum, and photoluminescence (PL). X-ray diffraction pattern shows the monoclinic cell of ZrS3 with the lattice constants a=5.128 Å, b=3.611 Å, c=9.012 Å, β=97.13°. The result of X-ray fluorescence gives a Zr(Hf):S mole ratio 1:2.97. The Raman spectrum of the ZrS3 nanocrystallites has a slightly red shift in comparison with that of ZrS3 single crystals. The room temperature photoluminescence of ZrS3 nanocrystallites is also reported.

High quality semiconducting famatinite (Cu3SbS4) nanofibers and tetradrite (Cu12Sb4S13) nanoflakes have been selectively synthesized through mild hydrothermal and solvothermal synthesis routes, respectively. The morphology and phase of the products can be successfully controlled by choosing appropriate reaction media to adjust the dynamics of the reaction process. It was found that reaction temperature is an important factor influencing the phase purity of the products. This method may provide a general route for the selective preparation of other semiconducting multinary sulfide nanocrystallites.

Metal sulfides MS (M=Cd, Zn, Co, Pb, Cu), M2S3 (M=Bi, Sb), M2S (M=Ag) were successfully synthesized through a one-step reaction between metal salts and thiourea in ethylene glycol (EG) under the microwave irradiation. The products were characterized by powder X-ray diffraction (XRD), X-ray photoelectron spectroscope (XPS), transmission electron microscope (TEM) and electron diffraction (ED).

The novel polygonal flake like Ag8SnS6 crystal, Cu2FeSnS4 flaky, and well-dispersed Cu2CoSnS4 nanoparticles were successfully prepared via a convenient hydrothermal reaction route at relatively low temperature, which was avoiding the use of high temperature treatments or toxic organic solvents. The products were characterized by means of X-ray powder diffraction (XRD), transmission electronic microscopy (TEM), X-ray photoelectronic spectra (XPS) and inductively coupled plasma-atomic emission spectroscopy (ICP-AES). It was found that the reaction temperature played a key role for the formation of the target products.

The synthesis of Ag nanoparticles from AgNO3 in acrylamide (AM) isopropyl alcohol solution has been achieved at room temperature by using an γ-irradiation reductive synthetic route in the field of a 2.22×1015 Bq γ-ray source at the dose rate of 50 Gy/min for 3–6 h. The initial concentration of AM, which could be polymerized as polyacrylamide (PAM) in irradiation field, played an important role in the morphologies of the Ag particles in solution. The Ag fractals were only obtained from the Ag clusters and particles in a dilute AM solution. These faceted Ag particles aggregate to from preferentially oriented Ag crystals with dispersed fractal morphologies, which could be ascribed to diffusion-limited aggregation (DLA) model on the amorphous carbon-coated copper grid. The fractal dimension of the Ag crystallites is between 1.70 and 1.75, which is close to that in DLA model simulation (1.70).

Different one-dimensional nickel sulfides, NiS nanorods and Ni9S8 nanorods were synthesized in the presence (Route 1) and absence (Route 2) of gas CO2. X-ray powder diffraction patterns, scanning electron microscopy and transmission electron microscopy images show that the product from Route 1 is NiS nanorods with a diameter of about 50–120 nm, while the product from Route 2 is Ni9S8 nanords about 70–200 nm in diameter. A molecular-template-like mechanism was proposed for the one-dimensional structures growth. The products were also investigated by Raman and photoluminescence (PL) spectroscopy.

In this report, a simple and easy polyol route for synthesizing many binary metal sulfides nanocrystallines is demonstrated. Powder X-ray electron diffraction and energy-dispersive X-ray spectrum are applied to investigate the crystallinity and composition of the nanoscale materials. The resulting particle size and morphology are examined by transmission electron microscopy, and the possible mechanism is also briefly discussed.

A simple and convenient polyol-mediated route has been developed to produce nanocrystalline Ag3SbS3 and Cu3SbS3 from AgNO3 and Cu(NO3)2 and SbCl3 with thiourea at 197 °C. The products were characterized by X-ray powder diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy. Analysis shows that glycol agitated state and injection rate have a great effect on the purity of the final products.

SnS2 films have been deposited on glass and alumina plate substrates by the reactions between an organotin precursor [tetrabuyltin, (CH2CH2CH2CH3)4Sn] and carbon disulfide in n-hexane at the temperature range 180–200 °C for 10–40 h. The reaction system was oxygen free and applied at a moderate temperature. The films so prepared were characterized by techniques of X-ray diffraction, Scanning electron microscopy, Raman and Mössbauer spectroscopies. The films deposited on glass as well as on alumina plate have an average thickness of 30 μm, but have different rose-like morphologies, which are influenced by both the anisotropic growths of crystals and the different substrate structures. Photoluminescence measurements show that the films have an emission peak at approximately 590 nm.

BiTeI submicrometer hollow spheres with diameters of 200–300 nm have been synthesized by an iodine transport hydrothermal method without the use of template materials or surfactants. The preparation was carried out in an autoclave in the temperature range 190–200 °C with Bi2Te3 and I2 as reactants. X-Ray powder diffraction patterns and transmission electron microscopy images show that the product is BiTeI with a hollow sphere structure. The sphere wall is composed of BiTeI nanoparticles with an average diameter of 5 nm and a thickness of ca. 10 nm. A possible growth mechanism for the hollow structure is proposed. The first excitonic peak of the BiTeI hollow spheres is considerably blue shifted in comparison with the band gap of the bulk material, which can be attributed to quantum confinement effects.

Nanocrystalline titanium carbonitride, TiC0.7N0.3, has been synthesized directly by a simple reaction route of TiCl4 and C3N3C13 using sodium as the reductant at 600°C. The composition of the powders has been investigated by X-ray powder diffraction. Transmission electron microscopy image reveals that the average size of the obtained particles is about 30 nm.

CaS and SrS nanocrystallites have been successfully synthesized via a solvothermal route by the reaction between XCl2 (X=Ca, Sr) and sulfur at relatively lower temperature for the first time. XS (X=Ca, Sr) nanocrystallites are efficient emission luminescence in comparison with that of bulk materials at room temperature. The emitted light of CaS and SrS nanocrystallites is yellow–green and blue, respectively.

The optical property of SnS2 nanocrystallites has been investigated by Raman scattering, far infrared spectrum and photoluminescence at room temperature. The Raman and far infrared spectrum of the SnS2 nanocrystallites have a shift in comparison with that of the SnS2 single crystals. The shift is mainly attributed to nanosize effect. The intralayer and interlayer force constant of SnS2 nanocrystallites have been calculated by using a linear chain model. The photoluminescence of SnS2 nanocrystallites is reported for the first time.

Antimony sulfide tetragonal (rectangular) prismatic tubular crystals with dimenions of 6–10 mm in length, 50–60 µm in width, and 5–15 µm in thickness were successfully synthesized for the first time via a hydrothermal reaction route from antimony trichloride and sodium thiosulfate in the presence of ammonium chloride at 198°C.

A simple solventothermal method has been employed for nanocrystalline MSe2 (M=Fe, Co or Ni) at 160°C. The final product phases were confirmed by X-ray diffraction (XRD). Transmission electron microscopy (TEM) revealed that the obtained crystalline MSe2 consist of nano-particles and a small amount of irregular plate-like products with relatively large size.

Millimeter-sized tubular crystals of Ag2Se are successfully grown for the first time via a hydrothermal reaction route from AgCl, Se and NaOH at 155 °C.

Monodisperse hollow and core-shell magnetite (Fe3O4) spheres have been prepared by a simple one-pot method based on hydrothermal treatment of FeCl3, citrate, polyacrylamide and urea. The as-prepared samples have been characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, nitrogen adsorption-desorption isotherms, superconducting quantum interference device magnetometer. The results of control experiments reveal that citrate and polyacrylamide are crucial for the formation of spherical product and the well known Ostwald ripening process is responsible for the transformation from solid spheres to hollow and core-shell spheres. The hollow and core-shell magnetite spheres are porous and highly water soluble. They exhibit superparamagnetic properties with relatively high saturation magnetization at room temperature. The superparamagnetic properties, high magnetization, high water solubility, together with the hollow interiors will render them ideal candidates for various biomedical applications.

HLaNb2O7 nanosheets and Ag nanoparticles/clusters were assembled to produce a novel 3D metal/semiconductor hybrid material (Ag/HLaNb2O7) by direct reaction of the undried D-glucopyranose derivative of HLaNb2O7 with [Ag(NH3)2]+ ion aqueous solution. The as-prepared samples were characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, UV-visible diffusive reflectance spectroscopy and nitrogen adsorption–desorption isotherms. The results showed that the simple self-assembly of HLaNb2O7 nanosheets and Ag nanoparticles/clusters formed a mesoporous material with a broad pore size distribution in the range of about 10–35 nm. The mesopores derived from the interspaces between HLaNb2O7 nanosheets and were attributed to Ag nanoparticles, rather than Ag clusters in the interlayer space of HLaNb2O7. The catalytic activity experiments revealed that the product (Ag/HLaNb2O7) was an excellent catalyst for the catalytic reduction of 4-nitrophenol (4-NP) and rhodamine B (RhB) by NaBH4 aqueous solution.

Carbon was successfully intercalated into the interlayer space of the Dion–Jacobson type layered perovskite HLaNb2O7 by pyrolysis of the precursor of a D-glucopyranose derivative of HLaNb2O7. Firstly, the D-glucopyranose derivative of HLaNb2O7 (D-glucopyranose-HLaNb2O7) was prepared by the grafting reaction between the n-decoxyl derivative of HLaNb2O7 and D-glucopyranose. The interlayer distance of D-glucopyranose-HLaNb2O7 was decreased to 15.4 Å, compared to that of 27.6 Å for n-decoxyl-HLaNb2O7. IR and solid-state 13C CP/MAS NMR spectra indicated that oxyalkyl chains were removed and glucopyranose rings were introduced. After pyrolysis of the D-glucopyranose derivative at 300 °C under flowing Ar, a novel intercalation compound of HLaNb2O7 with carbon (carbon-HLaNb2O7) was obtained. XRD pattern and HRTEM image both displayed the interlayer distance of about 12 Å. Raman and solid-state 13C CP/MAS NMR spectra revealed that the intercalated carbon was mainly polycyclic aromatic carbon. The UV-VIS-near-IR spectrum showed that the carbon-HLaNb2O7 appreciably absorbed light at wavelengths below 855 nm and the band gap energy was only about 0.65 eV, which was much smaller than those of HLaNb2O7 and its derivatives, indicating that the intercalation with carbon can effectively modify the band gaps of Dion–Jacobson type layered perovskites.

Monodisperse Cu2WO4(OH)2 round and elliptical hollow spheres have been successfully prepared by a ligand-assisted dissolution process, without any template or surfactant.

CdSnO3 materials have been extensively studied as gas-sensing materials. However, there are few reports on the synthesis and use of porous CdSnO3 nanostructures for energy storage. Herein, we report highly porous CdSnO3 nanoparticles prepared using citric acid with sizes in the range of ∼7.8 nm to 28.7 nm and the application of these nanoparticles as an anode material for rechargeable Li-ion batteries (LIBs). Electrochemical measurements showed that the highly porous CdSnO3 nanoparticles delivered a high reversible capacity of ∼515 mA h g−1 for up to 40 cycles at a current rate of 70 mA g−1. Even at a high rate of 150 mA g−1, the porous CdSnO3 could still deliver a capacity of 506 mA h g−1. It is observed that the electrochemical performance of the highly porous CdSnO3 nanoparticles is much better than that (∼370 mA h g−1 for up to 40 cycles) of a counterpart obtained without citric acid, which also demonstrates the capacity enhancement and high rate capacity.

D-Glucopyranose rings have been successfully coordinated onto the interlayer surface of a Ruddlesden–Popper-type layered perovskite, H2CaTa2O7, by a reaction with the precursor of n-decoxyl derivative of H2CaTa2O7. The interlayer distance of D-glucopyranose derivative of H2CaTa2O7 was decreased to 19.135(5) Å compared to 35.026(0) Å for n-decoxyl derivative of H2CaTa2O7. IR and solid-state 13C CP/MAS NMR spectra indicated that the oxyalkyl chains of the precursor were replaced by glucopyranose rings. To extend inorganic–organic hybrids, the H2CaTa2O7 modified was further treated with [Ag(NH3)2]+ solution. Ag nanoparticles are deposited on the interlayer of H2CaTa2O7, and the interlayer distance of the samples is changed into 10.816(6) Å. The as-prepared nanohybrids (Ag/H2CaTa2O7) exhibit an excellent catalytic property for the catalytic reduction of both rhodamine B (RhB) and 4-nitrophenol (4-NP) by NaBH4 aqueous solution; therefore, it is a practical and efficient nanocatalyst.

In this work, nanocrystalline-assembled bundle-like CuO structures were successfully synthesized in large-quantity by a friendly, facile two-step process. The bundle-like CuO particles are produced by thermolysis of bundle-like Cu(OH)2 precursors, which exhibit excellent high specific capacity, high stability, and especially high rate performance for anode materials in lithium-ion batteries, superior to that of most reported CuO-based anodes. The assembled structure of CuO endows it with high rate capacities of 666 mAh g−1, 609 mAh g−1, and 499 mAh g−1 at a current rate of 0.3 C, 1 C and 2 C after 50 cycles, respectively. Even at a high rate of 6 C, the bundle-like CuO can still deliver a capacity of 361 mAh g−1. It is observed that the electrochemical performance of the nanocrystalline-assembled bundle-like CuO is much better than that of CuO nanoparticles obtained by destroying the assembled bundle-like CuO through grinding. XRD analysis of both the electrodes after ending the discharge/charge proved that during the discharge/charge process, the conversion reactions occurring in the assembled structures have better reversibility, leading to the high rate capacity and cycling performances. The better reversibility originates from the better contact area for CuO/electrolyte, enhancing many sites to the access of Li+ in the electrolyte Li+. In addition, the assembled bundle-like CuO architectures can also relieve the volume variations during the Li+ uptake–release process, which also contributes to the excellent electrochemical performance. The high rate capacity and enhanced cycling stability of the bundle-like CuO structure make it a promising candidate as an anode material for high-performance Li-ion batteries.

The synthesis of single-crystalline hollow particles with well-defined non-spherical shapes, especially hollow complex compounds, remains a significant challenge. In this paper, single-crystalline ZnSn(OH)6 (ZHS) hollow cubes were first synthesized by a facile self-templating method at room temperature. On the basis of X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy and transmission electron microscopy, it was found that hollow ZHS cubes were formed by a two-step process, in which solid cubes of ZHS were formed in the first step due to the co-precipitation of Zn(II) and Sn(IV) under basic conditions and then the solid cubes as the self-templates were converted to hollow ones through an alkali-assisted dissolution process. During the process, NaOH solution added in the second step is critical to the formation of ZHS hollow structures. The photocatalytic activity of ZHS hollow cubes for phenol degradation was tested, which showed much higher catalytic activity than that of the solid ZHS cubes. After four trials, the photocatalytic activity of the ZHS hollow cubes exhibits no significant loss.