•F-SnO2/rGO was synthesized through a hydrothermal method.•F-SnO2 nanoparticles were uniformly anchored on the surfaces of rGO sheets.•Electrical conductivity and Li-ion diffusion were remarkably improved.•The composite material exhibited superior performance in Li-ion batteries.The composite of fluorine-doped SnO2 anchored on reduced graphene oxide (F-SnO2/rGO) has been synthesized through a hydrothermal method. F-SnO2 particles with average size of 8 nm were uniformly anchored on the surfaces of rGO sheets and the resulting composite had a high loading of F-SnO2 (ca. 90%). Benefiting from the remarkably improved electrical conductivity and Li-ion diffusion in the electrode by F doping and rGO incorporation, the composite material exhibited high reversible capacity, excellent long-term cycling stability and superior rate capability. The electrode delivered a large reversible capacity of 1037 mAh g−1 after 150 cycles at 100 mA g−1 and high rate capacities of 860 and 770 mAh g−1 at 1 and 2 A g−1, respectively. Moreover, the electrode could maintain a high reversible capacities of 733 mAh g−1 even after 250 cycles at 500 mA g−1. The outstanding electrochemical performance of the as-synthesized composite make it a promising anode material for high-energy lithium ion batteries.Download high-res image (442KB)Download full-size image

•A two steps method was utilized to synthesis the composite and the composition and structure of the composite is novel.•The exploration of the composite from ternary to quaternary composite is meaningful.•The mechanism of the photocatalytic process provide a new visual for the exploration of photocatalyst.A series of novel and facile quaternary composite BiVO4/MWCNT/Ag@AgCl were synthesized through hydrothermal and in situ oxidization method. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV–vis diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TG), Brunauer Emmett Teller surface area (BET), and Raman scattering spectroscopy were utilized to characterize the as-mentioned quaternary composite. The catalytic performance of the composite was investigated by the degradation of 5 mgL−1 rhodamine B (RhB) under visible light irradiation (λ ≥ 420 nm). The weight ratio of Ag and the mole ratios of Ag to AgCl in the composite can influence the photocatalytic performance. When the weight ratio of Ag is 20% and the mole ratio of AgNO3 to FeCl3 is 4: 1, the catalyst exhibits much superior visible light catalytic activity than pure BiVO4 and it can decompose 99% of RhB in 100 min.

Graphene wrapped 3,4,9,10-perylenetetracarboxylic dianhydride (C24H8O6) composite materials have been successfully prepared through a facile heat-treatment process at different temperatures. Benefiting from the three-dimensional conductive network provided by the densely distributed graphene nanoplates, the composite material exhibits a high reversible capacity, an excellent cycling stability and a superior rate capability. When cycled against lithium in the potential range of 1.5 to 4.6 V, the composite material prepared at 400 °C exhibited an increasing discharge capacity at 100 mA g−1 with a maximum value of 172 mA h g−1 at the 180th cycle. In addition, the material is able to deliver reversible capacities of 152, 144, 134 and 110 mA h g−1 at high current densities of 200, 300, 500 and 1000 mA g−1, respectively, with 98% of the capacity retained after 200 cycles at 500 mA g−1. The excellent electrochemical properties of the composite material make it a promising organic cathode material for large-scale lithium ion batteries.

•Na2FePO4F/C composite was synthesized by carbothermal reduction method.•Mixed carbon source could form highly graphitized carbon.•Conductivity was remarkably improved by the thin carbon layer.•The synthesized Na2FePO4F/C exhibits good electrochemical performances.•Electrochemical kinetic characteristic of NaLiFePO4F/C was investigated by EIS.Carbon coated spherical Na2FePO4F particles with typical diameters from 500 nm to 1 μm have been synthesized through an economical carbothermal reduction method with a simple apparatus. Mixed carbon source consists of citric acid and phenolic resin can form highly graphitized carbon and remarkably improve the electrical conductivity. When cycled against lithium, Na2FePO4F/C cathodes deliver maximum discharge capacity of 119 mAh g−1 at a low rate of 0.05 C. Reversible capacity of 110 mAh g−1, 74 mAh g−1 and 52 mAh g−1 can be obtained at 0.1 C, 1 C and 2 C rates, respectively. And after 30 cycles at 0.1 C, 91% of the discharge capacity can still be maintained. The electrochemical kinetic characteristic of electrode material is investigated by EIS and the apparent Li+ diffusion coefficient in the Li/Na2FePO4F system is evaluated to be as high as 1.152 × 10−11 cm2 s−1. This study demonstrates that the practical and economical synthesis process can be a promising way for industrial production of high performance Na2FePO4F/C electrode material for large-scale lithium ion batteries.

Micro/nano-structured polyaniline/silver (PANI/Ag) composites have been prepared by simply mixing nitric acid doped polyaniline with silver nitrate. A reducing agent was added to accelerate the reaction process and enhance the conversion rate of silver nitrate. As the support material of silver nanoparticles, nitric acid doped polyaniline was synthesized under turbulent flow and surfactants were adopted to control the morphology and uniformity of the particles. Various analysis techniques were adopted to confirm the composition and structure of the composites, including scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectrometry (FTIR) and energy dispersive X-ray analysis (EDX). The PANI/Ag particles were used as a catalyst in the borohydride reduction reaction of 4-nitrophenol (4-NP), which was online monitored by UV-vis absorption spectroscopy. Results demonstrated that PANI microspheres loaded with 18.30 wt% of silver showed a comparable catalytic performance, and the apparent rate constant is 0.0256 s−1. Moreover, the stability and reusability of the catalyst were also investigated. The present work highlights the incorporation of well-dispersed silver nanoparticles with the conductive polyaniline matrix, and the accelerated electron transfer during the catalytic process owing to the high electrical conductivity of the support material.

A series of highly efficient and low cost visible light-driven micro/nano-structure photocatalysts, composed of microstructure SiO2 spheres and Ag/AgCl nanocomposites with different proportion of AgCl to Ag, have been facilely and controllably fabricated via deposition–precipitation method and in situ oxidation process. The obtained samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), energy dispersive spectrometry (EDS), X-ray photoelectron spectroscopy (XPS) and UV-vis diffuse reflectance spectra (UV-vis-DRS). The as-prepared photocatalysts exhibit wide absorption in the visible light region and display superior photocatalytic activity and excellent stability towards degradation of organic pollutants, i.e., rhodamine B (RhB) compared with commercial TiO2 (P25) and pure Ag/AgCl under visible light (λ ≥ 420 nm). Furthermore, the molar ratio of AgCl to Ag in the SiO2@Ag/AgCl composites has an important effect on their photocatalytic performance. The possible mechanism for the enhancement in decomposition of RhB molecules under visible light irradiation is discussed. This work may provide new insights into the fabrication of visible light-driven photocatalysts with low cost and excellent performance and facilitate their practical application in environmental issues.

Here we present a cheap alternative for the fabrication of conductive line patterns printed on a flexible PI substrate at intermediate temperature. In order to achieve this purpose, a low-cost and water-soluble screen printing conductive paste was prepared, with micron-SiO2@nano-Ag particles as the conductive filler. Variations in the filling content of micron-SiO2@nano-Ag, the addition of the coupling agent, curing temperature and time can remarkably affect the electrical and mechanical performance of the conductive paste. The optimal sheet resistance (at 62 mΩ □−1) and mechanical performance of the paste were achieved under the curing conditions of 140 °C for 30 min, with the filling content of 53.6 wt% of micron-SiO2@nano-Ag (32.4 wt% of Ag) and 1.0 wt% of the coupling agent APTES. The conductive mechanism of the paste was discussed according to the “percolation theory”. The conductive line patterns fabricated through silk-screen printing were applied to be linked with a LED into a circuit, suggesting that the paste would have a potential application in electronic devices.

A novel organic salt, namely (H2PO3)2·(H3PO3)·(phenH)2·H2O (1), is synthesized and characterized, and shows a 3D tessellate-type supramolecular structure containing 1D [(phenH+)·(H2PO3−)]n supramolecular chains. Compound 1 is a multifunctional material: it displays infrequent water/humidity-induced fluorescence switching performance at room temperature, whose fluorescent color can be reversibly changed between blue, cyan and violet by placing at different relative humidities or adding various amounts of water; moreover, compound 1 shows interesting heat-induced coloration at high temperature, whereby its color can be changed from colorless to red by heat. The mechanisms of the fluorescence switching and coloration are also investigated.

Two novel epoxy resins; namely, R1 and R2 were synthesized and characterized. These two resins were isomers and both contained naphthalene units and two symmetric flexible aliphatic ester chains terminated by epoxy groups. To investigate the influence of different structural isomers on the performance of these epoxy resins, they were both cured with various curing agents which results in the choosing of 4,4′-diaminodiphenylmethane (DDM) as the optimized curing agent. The curing technical temperature was obtained from extrapolated plots of T–β curve at different heating rates. The kinetic parameters, the activation energy (Ea) and the reaction order (n) were deduced by Kissnger’s isoconversional method and Crane equation. The moisture absorption and mechanical and thermal properties of the cured epoxy resins were investigated. Experimental results indicated that the R1/DDM and R2/DDM epoxy resins displayed improved mechanical performance without significant decrease in their important inherent properties, e.g., temperature of glass transition (Tg), moisture absorption and thermal properties when compared with the corresponding commercial biphenyl-type epoxy resins. The average inter-segment distances in R1/DDM and R2/DDM systems were 4.46 and 4.88 Å, respectively, which were measured by wide-angle X-ray diffraction. The result showed R1/DDM (1,5-di-substituted) was strongly hindered in comparison with R2/DDM (2,7-di-substituted) and Ea and Tg values of the R1/DDM were slightly higher than those of R2/DDM. Furthermore, mechanical properties and moisture absorption of the R1/DDM were lower than those of R2/DDM. Nevertheless, the position of the substituent only weakly affected the thermal properties and the reaction order (n).

A novel supramolecular plaster, (AEDPH3)·(BtaH) (1), is synthesised and characterized. The supramolecular plaster is easy to synthesise and process, and displays good mechanical properties. It can adsorb and eliminate formaldehyde (HCHO) with high efficiency and exhibits very interesting HCHO/ultraviolet ray-induced luminescence switching.

A novel supramolecular resin, namely, α-(AEDPH2)·(enH2)·3H2O (1) (AEDPH2 = 1-aminoethylidenediphosphonic acid and en = ethylenediamine), is synthesized and characterized by infrared (IR) spectroscopy, thermogravimetric analysis (TGA), elemental analysis (EA), single crystal X-ray diffraction (SCD), and powder X-ray diffraction (PXRD). The supramolecular resin is an organic acid−base compound and shows a three-dimensional (3D) tessellate-type supramolecular structure constructed via various hydrogen bonds, which contains a kind of D3 water cluster. It has good mechanical properties as well as excellent flame retardant performance. In addition, the supramolecular resin can form a single crystal, namely, β-(AEDPH2)·(enH2)·3H2O (2), by an interesting gel-to-crystal transformation. Compound 2 is the isomer of 1 which illustrates a sandwich-type supramolecular architecture contained an R4 water cluster.

A novel supramolecular plaster, namely (AEDPH3)·(1,2,4-tzH)·(H2O) (1), is synthesized and characterized by infrared spectrum (IR), thermogravimetric analysis (TGA), scanning electron microscope (SEM), elemental analysis (EA), single-crystal X-ray diffraction (SCD), and powder X-ray diffraction (PXRD). The supramolecular plaster is an organic acid−base compound and shows a three-dimensional (3D) sandwich typed supramolecular structure constructed via various hydrogen bonds. The supramolecular plaster has good sterilizing performance as well as excellent mechanical properties similar to the general gypsum plaster widely used in our daily life. The experimental results also prove that the supramolecular material based on hydrogen bonded assembly of small molecules has good mechanical properties.

A novel supramolecular plaster, namely (AEDPH3)·(ureaH)·(H2O) (1), is synthesized and characterized by infrared spectrum (IR), thermogravimetric analysis (TGA), elemental analysis (EA), single-crystal X-ray diffraction (SCD), and powder X-ray diffraction (PXRD). The supramolecular plaster is an organic acid−base compound that shows a 3D hydrogen-bonded supramolecular network with extended 1D channels. It is simple to synthesize and process and shows good mechanical properties similar to the gypsum-based plaster. Moreover, it has nice gas adsorption performance.

2D and 3D nano/microstructures of 4ZnO·B2O3·H2O with different morphologies have been successfully synthesized by a hydrothermal route in the presence of surfactant polyethylene glycol-300 (PEG-300). Lamellar-like nanoparticles and microsphere organizations of nano and microrods are fabricated by varying the reaction conditions. The products have been characterized by XRD, FT-IR, TG–DTA and SEM. The XRD data indicate the as-prepared samples present at pure phase 4ZnO·B2O3·H2O with monoclinic symmetry. The SEM results reveal that the lamellar-like particles are about 30 nm in thickness and around several hundred nanometers in diameter. The microsphere organizations have different diameters, and the secondary structures are made from rod-like particles with different size and mode, respectively. The morphologies of products strongly depend on surfactant, hydrothermal temperature and time.2D and 3D nano/microstructures with different morphologies of an industrially important zinc borate, 4ZnO·B2O3·H2O, have been prepared by the hydrothermal method using PEG-300 as soft template. By controlling the reaction conditions, lamellar-like nanoparticles and microsphere organizations of nano and microrods have been prepared. The effect of reaction conditions and the growth mechanism has been proposed.

Hexagonal ZnO micronuts (HZMNs) have been successfully synthesized with the assistance of poly(ethylene glycol) (PEG) 300 via a hydrothermal method. The structure and morphology of the HZMNs were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and selected area electron diffraction (SAED). An individual ZnO micronut is revealed as twinned crystals. Time-dependent investigation shows that the growth of HZMNs involves a dissolution−recrystallization process followed by Ostwald ripening, in which is the first formed solid ZnO particles dissolve and transform to HZMNs with hollow structure. PEG 300 has been found to play a crucial role in the growth of this unique hollow structure. TEM observations show that the PEG chains aggregate to globules in water, which then have interaction with the dissolved zinc species to form the globules in a coiled state under hydrothermal conditions. These Zn(II)-PEG 300 globules act as soft template for the growth of HZMNs, and the possible growth mechanism is proposed. The room-temperature photoluminescence (PL) spectrum shows red emission around 612 nm with a full width at half-maximum (fwhm) only about 13 nm.

A new in situ low-temperature, low-pressure hydrothermal condensation reaction of amino diphosphonic acids affords a series of phosphonate derivatives with bicyclic structures. By using such bicyclic phosphonate ligands, three compounds, namely, [Zn2(L1)(phen)4]·12H2O (1), [Ni(Im)6]3(L2)2(ImH)2·24H2O (2), and [Cu2(L3)(phen)2(H2O)2]·9H2O (3) (phen = 1,10-phenanthroline, Im = imidazole, L1H4, L2H4, and L3H4 represent different bicyclic phosphonate derivatives), have been synthesized and structurally characterized by single-crystal X-ray crystallography. Novel water clusters with different structural motifs, such as T4(3)5(0)A0 water tape in 1, TU water tape in 2, and L5(4)5(5)15(14) water layer in 3, are discussed in detail. The coordination mode of the metal ion and the use of the appropriate second ligand, which would influence the reaction and structures of the final products are also discussed.

This paper developed a novel method, the rheological phase reaction method, to synthesize nanospherical Fe3BO6. The sizes and morphologies of products vary with the calcination temperatures. Spherical particles with a uniform size about 40 nm in a monodisperse state were obtained at 800 °C, while the spherical particles with a larger size of 100–500 nm were obtained at 900 °C. The electrochemical properties of these Fe3BO6 nanospheres were investigated. Sample synthesized at 800 °C delivers a high reversible capacity above 500 mAh g−1. Sample synthesized at 900 °C possesses relatively good cycleability with a capacity retaining of 376 mAh g−1 after 10 cycles. The measurement of electrochemical impedance spectra for the first time indicated that smaller Fe3BO6 nanoparticles intend to give higher impedance of solid-electrolyte interface layer and lower charge-transfer impedance after the first discharge. Additionally, it can be speculated that the increase of resistance charge-transfer is the possible reason for the capacity fading during cycling.Nanospherical Fe3BO6 anode material for lithium-ion battery has been synthesized by the rheological phase reaction method. The electrochemical properties of these Fe3BO6 nanospheres show that sample synthesized at 800 °C delivers a high reversible capacity above 500 mAh g–1, and sample synthesized at 900 °C possesses relatively good cycleability with a capacity retaining of 376 mAh g−1 after 10 cycles.

Hydrothermal reaction of 1-amino-1-phenylmethane-1,1-diphosphonic acid (APhMDPH4), ZnO and 2,2′-bipyridyl (2,2-bipy) affords a novel zinc phosphonate compound, i.e. Zn3(L1H)2(2,2′-bipy)3 · 18H2O (1), in which the phosphonate ligand, L1H4, is generated via an in situ concentration reaction. This compound is a one-dimensional (1D) zigzag coordination polymer chain and a huge, complex 1D water column. The 1D water column and the 1D coordination polymer chain are joined together to form a vertical interpenetrating network, which is reported for the first time.

Hydrothermal reactions of 1-aminoethylidenediphosphonic acid (AEDPH4), imidazole (Im) and divalent metal oxides afforded two novel phosphonate compounds: Zn2(AEDP)(Im)3·H2O (1), Cd3(AEDPH)2(Im)5·Im (2). Compounds 1 and 2 are both one-dimensional (1-D) coordination polymers that illustrate different chain motifs. Compound 1 features a zigzag double chain structure while compound 2 has a distorted square-chain structure. Both compounds are further extended to form three-dimensional (3-D) supramolecular structures via hydrogen bonds. The effect of degree of deprotonization of AEDPH4 on the structural types of the final products is also discussed.

Two europium α-thiophene carboxylic acid (HTPA) compounds, coordination polymer Eu(TPA)3(HTPA)2 (1) (TPA=α-thiophene carboxylate) and supramolecular compound Eu(TPA)3(H2O)3 · 0.5H2O (2) with luminescence and triboluminescence, have been synthesized and structurally characterized. In 1 each europium is bridged by six oxygen atoms from six carboxylates and coordinated with two carboxyl oxygen atoms from two α-thiophene carboxylic acid molecules, resulting in a coordination number of eight to Eu. For 2 each europium is chelated by six oxygen atoms from six carboxylates and coordinated with three oxygen atoms from three coordinated water generating a coordination number nine to Eu; A supramolecular compound is constructed through hydrogen bonds. Both 1 and 2 display strong characteristic emission of Eu3+ ion radiated by UV light and produce twinkling red light with an external force.Two europium α-thiophene carboxylic acid (HTPA) compounds, coordination polymer Eu(TPA)3(HTPA)2 (1) (TPA = α-thiophene carboxylate) and supramolecular compound Eu(TPA)3(H2O)3 · 0.5H2O (2) with luminescence and triboluminescence have been synthesized and structurally characterized. Both 1 and 2 display strong characteristic emission of Eu3+ ion radiated by UV light and produce twinkling red light with a outside force.

Three new aminodiphosphonates, namely M(phen)(AEDPH3)2·4H2O (M = Zn, (1); Ni, (2)) and Cu(phen)(AEDPH3)2·H2O (4), in addition to the previously reported Co(phen)(AEDPH3)2·4H2O (3), Cu(2,2′-bipy)(H2O)(HEDPH2)·2H2O (5), and Cu(phen)(H2O)(HEDPH2)·2H2O (6) (AEDPH4 = 1-aminoethylidenediphosphonic acid, HEDPH4 = 1-hydroxyethylidenediphosphonic acid, phen = 1,10-phenanthroline and 2,2′-bipy = 2,2′-bipyridyl), have been synthesized and characterized. These compounds are all synthesized at the similar condition (80 °C), whereas they illustrate different frameworks. Compounds 1, 2 and 3 are isomorphous, which contain two same chelate AEDPH3- and one six-coordinated metal ion, and display a three-dimensional (3D) supramolecular structure through hydrogen bonds and π–π stacking interactions. Compound 4 contains a chelate and a monodentate AEDPH3-, while the Cu ion is five-coordinated. The coordination model of Cu2+ in 4 is similar to that of 5 and 6. Comparing with four aminoethylidenediphosphonates, the difference of their structures is directed to the coordination model of the metal ions, while the three copper(II) diphosphonates illustrate different structures based on the deprotonized degree of the corresponding diphosphonic acids.

Graphene wrapped 3,4,9,10-perylenetetracarboxylic dianhydride (C24H8O6) composite materials have been successfully prepared through a facile heat-treatment process at different temperatures. Benefiting from the three-dimensional conductive network provided by the densely distributed graphene nanoplates, the composite material exhibits a high reversible capacity, an excellent cycling stability and a superior rate capability. When cycled against lithium in the potential range of 1.5 to 4.6 V, the composite material prepared at 400 °C exhibited an increasing discharge capacity at 100 mA g−1 with a maximum value of 172 mA h g−1 at the 180th cycle. In addition, the material is able to deliver reversible capacities of 152, 144, 134 and 110 mA h g−1 at high current densities of 200, 300, 500 and 1000 mA g−1, respectively, with 98% of the capacity retained after 200 cycles at 500 mA g−1. The excellent electrochemical properties of the composite material make it a promising organic cathode material for large-scale lithium ion batteries.

A novel supramolecular plaster, (AEDPH3)·(BtaH) (1), is synthesised and characterized. The supramolecular plaster is easy to synthesise and process, and displays good mechanical properties. It can adsorb and eliminate formaldehyde (HCHO) with high efficiency and exhibits very interesting HCHO/ultraviolet ray-induced luminescence switching.