Photocatalytic degradation of bisphenol A and dye by graphene-oxide/Ag3PO4 composite under visible light irradiation

A facile, one-step synthesis of graphene-oxide (GO)/Ag₃PO₄ was prepared. The as-prepared samples were characterized by scanning electron microscopy (SEM), energy dispersive spectrometer (EDS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS) and fourier transformed infrared (FT-IR) spectroscopy. The SEM image indicated that Ag₃PO₄ particles were mainly distributed on the surface of GO sheets uniformly. DRS analysis revealed that the samples had good visible light response. The photocatalytic activity of the composites was evaluated by the degradation of Rhodamine B (RhB) and Bisphenol A (BPA). The results indicated that the photocatalytic performance of GO/Ag₃PO₄ was greatly enhanced after introduction of GO. The photocatalytic degradation efficiency of colorless chemical pollutants (BPA) over GO/Ag₃PO₄ was higher than that of Ag₃PO₄, and the possible degradation path was proposed by liquid chromatography mass spectrometry (LC-MS) analysis. Moreover, the photocatalytic stability was discussed by XRD and FT-IR spectroscopy analysis. Based on the experimental results, a possible visible-light photocatalytic degradation mechanism was also discussed.     

Lithium insertion in ultra-thin nanobelts of Ag2V4O11/Ag

In this study, ultra-thin nanobelts of Ag₂V₄O₁₁/Ag were successfully synthesized. The synthesized ultra-thin nanobelts of Ag₂V₄O₁₁/Ag are highly crystalline and the thickness is found to be about 5 nm. A lithium battery using ultra-thin nanobelts of Ag₂V₄O₁₁/Ag as the active materials of the positive electrode exhibits a high initial discharge capacity of 276 mAh g⁻¹, corresponding to the formation of Li_xAg₂V₄O₁₁ (x = 6). With increased cycling, the electrode made of ultra-thin nanobelts of Ag₂V₄O₁₁/Ag tends to loose electrochemical activity due to Ag⁺ ions in the ultra-thin nanobelts of Ag₂V₄O₁₁ were reduced and new phase was formed.     

Synthesis and electrochemical properties of Co-doped Li3V2(PO4)3 cathode materials for lithium-ion batteries

Co-doped Li₃V_2−xCo_x(PO₄)₃/C (x = 0.00, 0.03, 0.05, 0.10, 0.13 or 0.15) compounds were prepared via a solid-state reaction. The Rietveld refinement results indicated that single-phase Li₃V_2−xCo_x(PO₄)₃/C (0 ≤ x ≤ 0.15) with a monoclinic structure was obtained. The X-ray photoelectron spectroscopy (XPS) analysis revealed that the cobalt is present in the +2 oxidation state in Li₃V_2−xCo_x(PO₄)₃. XPS studies also revealed that V⁴⁺ and V³⁺ ions were present in the Co²⁺-doped system. The initial specific capacity decreased as the Co-doping content increased, increasing monotonically with Co content for x > 0.10. Differential capacity curves of Li₃V_2−xCo_x(PO₄)₃/C compounds showed that the voltage peaks associated with the extraction of three Li⁺ ions shifted to higher voltages with an increase in Co content, and when the Co²⁺-doping content reached 0.15, the peak positions returned to those of the unsubstituted Li₃V₂(PO₄)₃ phase. For the Li₃V_1.85Co_0.15(PO₄)₃/C compound, the initial capacity was 163.3 mAh/g (109.4% of the initial capacity of the undoped Li₃V₂(PO₄)₃) and 73.4% capacity retention was observed after 50 cycles at a 0.1 C charge/discharge rate. The doping of Co²⁺into V sites should be favorable for the structural stability of Li₃V_2−xCo_x(PO₄)₃/C compounds and so moderate the volume changes (expansion/contraction) seen during the reversible Li⁺ extraction/insertion, thus resulting in the improvement of cell cycling ability.     

A promising sol-gel route based on citric acid to synthesize Li3V2(PO4)3/carbon composite material for lithium ion batteries

Li₃V₂(PO₄)₃/carbon composite material was synthesized by a promising sol-gel route based on citric acid using V₂O₅ powder as a vanadium source. Citric acid acts not only as a chelating reagent but also as a carbon source, which enhance the conductivity of the composite material and hinder the growth of Li₃V₂(PO₄)₃ particles. The structure and morphology of the sample were characterized by TG, XRD and TEM measurements. XRD results reveal that Li₃V₂(PO₄)₃/carbon was successfully synthesized and has a monoclinic structure with space group P2₁/n. TEM images show Li₃V₂(PO₄)₃ particles are about 45 nm in diameter embeded in carbon networks. Galvanostatic charge/discharge and cyclic voltammetry measurements were used to study its electrochemical behaviors which indicate the reversibility of the lithium extraction/insertion processes. Li₃V₂(PO₄)₃/carbon performed in a voltage window (3.0-4.8 V) exhibits higher discharge capacity, better cycling stability and its discharge capacity maintains about 167.6 mAh/g at a current density of 28 mA/g after 50 cycles.     

Mechanochemical synthesis of kaolin-KH2PO4 and kaolin-NH4H2PO4 complexes for application as slow release fertilizer

A milling process to reduce kaolin to amorphous phase in the presence of KH₂PO₄ or NH₄H₂PO₄ and allow mechanochemical (MC) reaction for incorporation of KH₂PO₄ and NH₄H₂PO₄ into the kaolin structure was investigated in this work. Mixtures of kaolin and KH₂PO₄ and NH₄H₂PO₄ in separate systems were prepared by milling in a planetary ball mill. Tests with kaolin contents ranging from 25 to 75 wt.% and mill rotational speeds from 200 to 700 rpm were performed to evaluate incorporation of KH₂PO₄ and NH₄H₂PO₄ and release of K⁺, NH₄⁺ and PO₄³⁻ ions into solution. Analyses by XRD, DTA and ion chromatography indicated that the MC process was successfully applied to incorporate both KH₂PO₄ and NH₄H₂PO₄ into the amorphous kaolin structure. Release of K⁺ and PO₄³⁻ ions from the system (kaolin-KH₂PO₄) when dispersed in water for 24 h reached only up to 10%. Under similar conditions for the system (kaolin-NH₄H₂PO₄), release of NH₄⁺ and PO₄³⁻ ions reached between 25 and 40%. These results indicated that the MC process can be developed to allow amorphous kaolin to act as a carrier of K⁺, NH₄⁺ and PO₄³⁻ nutrients to be released slowly for use as fertilizer.     

Ag3PO4 quantum dot sensitized BiPO4: A novel p–n junction Ag3PO4/BiPO4 with enhanced visible-light photocatalytic activity

Ag₃PO₄ quantum dot sensitized BiPO₄, a novel p–n junction Ag₃PO₄/BiPO₄ photocatalyst, was prepared by co-precipitation hydrothermal method and characterized by XRD, XPS, SEM, TEM, HRTEM, EDS and DRS. Ag₃PO₄/BiPO₄ exhibited much higher photocatalytic activity than Ag₃PO₄ and BiPO₄ for the degradation of methyl orange under visible light (λ > 420 nm). The enhanced photocatalytic activity of Ag₃PO₄/BiPO₄ could be mainly ascribed to the strong visible-light absorption originating from the quantum dot sensitization of Ag₃PO₄ and high efficient separation of photogenerated electron–hole pairs through Ag₃PO₄/BiPO₄ heterojunction. Moreover, O₂⁻ and OH were the main reactive species.     

Comparison of AlPO4- and Co3(PO4)2-coated LiNi0.8Co0.2O2 cathode materials for Li-ion battery

Electrochemical and thermal properties of Co₃(PO₄)₂- and AlPO₄-coated LiNi_0.8Co_0.2O₂ cathode materials were compared. AlPO₄-coated LiNi_0.8Co_0.2O₂ cathodes exhibited an original specific capacity of 170.8 mAh g⁻¹ and had a capacity retention (89.1% of its initial capacity) between 4.35 and 3.0 V after 60 cycles at 150 mA g⁻¹. Co₃(PO₄)₂-coated LiNi_0.8Co_0.2O₂ cathodes exhibited an original specific capacity of 177.6 mAh g⁻¹ and excellent capacity retention (91.8% of its initial capacity), which was attributed to a lithium-reactive Co₃(PO₄)₂ coating. The Co₃(PO₄)₂ coating material could react with LiOH and Li₂CO₃ impurities during annealing to form an olivine Li_xCoPO₄ phase on the bulk surface, which minimized any side reactions with electrolytes and the dissolution of Ni⁴⁺ ions compared to the AlPO₄-coated cathode. Differential scanning calorimetry results showed Co₃(PO₄)₂-coated LiNi_0.8Co_0.2O₂ cathode material had a much improved onset temperature of the oxygen evolution of about 218 °C, and a much lower amount of exothermic-heat release compared to the AlPO₄-coated sample.     

Low temperature solid-state synthesis routine and mechanism for Li3V2(PO4)3 using LiF as lithium precursor

Monoclinic lithium vanadium phosphate, Li₃V₂(PO₄)₃, has been successfully synthesized using LiF as lithium source. The one-step reaction with stoichiometric composition and relative lower sintering temperature (700 °C) has been used in our experimental processes. The solid-state reaction mechanism using LiF as lithium precursor has been studied by X-ray diffraction and Fourier transform infrared spectra. The Rietveld refinement results show that in our product sintered at 700 °C no impurity phases of VPO₄, Li₅V(PO₄)₂F₂, or LiVPO₄F can be detected. The solid-state reaction using Li₂CO₃ as Li-precursor has also been carried out for comparison. X-ray diffraction patterns indicate that impurities as Li₃PO₄ can be found in the product using Li₂CO₃ as Li-precursor unless the sintering temperatures are higher than 850 °C. An abrupt particle growth (about 2 μm) has also been observed by scanning electron microscope for the samples sintered at higher temperatures, which can result in a poor cycle performance. The product obtained using LiF as Li-precursor with the uniform flake-like particles and smaller particle size (about 300 nm) exhibits the better performance. At the 50th cycle, the reversible specific capacities for Li₃V₂(PO₄)₃ measured between 3 and 4.8 V at 1C rate are found to approach 147.1 mAh/g (93.8% of initial capacity). The specific capacity of 123.6 mAh/g can even be hold between 3 and 4.8 V at 5C rate.     

Structure and electrochemical properties of nanocarbon-coated Li3V2(PO4)3 prepared by sol-gel method

A liquid-based sol-gel method was developed to synthesize nanocarbon-coated Li₃V₂(PO₄)₃. The products were characterized by XRD, SEM and electrochemical measurements. The results of Rietveld refinement analysis indicate that single-phase Li₃V₂(PO₄)₃ with monoclinic structure can be obtained in our experimental process. The discharge capacity of carbon-coated Li₃V₂(PO₄)₃ was 152.6 mAh/g at the 50th cycle under 1C rate, with 95.4% retention rate of initial capacity. A high discharge capacity of 184.1 mAh/g can be obtained under 0.12C rate, and a capacity of 140.0 mAh/g can still be held at 3C rate. The cyclic voltammetric measurements indicate that the electrode reaction reversibility is enhanced due to the carbon-coating. SEM images show that the reduced particle size and well-dispersed carbon-coating can be responsible for the good electrochemical performance obtained in our experiments.     

Synthesis,performance and action mechanism of carbon black/Ag3PO4 photocatalysts

Novel carbon black (CB)/Ag₃PO₄ compound photocatalysts were synthesized from a hydrothermal method and characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy and electrochemical methods. The photocatalytic oxidation ability of CB/Ag₃PO₄ was evaluated through methyl orange degradation experiments under visible light irradiation. The CB/Ag₃PO₄ showed higher photocatalytic activity than pure Ag₃PO₄. It was indicated the compound catalysts could absorb and utilize more optical energy to improve the photocatalytic activity, which was attributed to the ability of carbon black to accelerate the electron-hole separation. In particular, the methyl orange photocatalytic degradation rate over the 7?mg/L CB/Ag₃PO₄ was 1.6 times that of Ag₃PO₄. And the results of the cyclic experiment show that the photocatalyst has good stability. Moreover, the mechanism about the photocatalytic activity of CB/Ag₃PO₄ compounds was investigated. In this photocatalytic reaction, ?OH was the major active substrate responsible for the visible-light-driven degradation.     

Electrochemical performance of the carbon coated Li3V2(PO4)3 cathode material synthesized by a sol-gel method

A carbon coated Li₃V₂(PO₄)₃ cathode material for lithium ion batteries was synthesized by a sol-gel method using V₂O₅, H₂O₂, NH₄H₂PO₄, LiOH and citric acid as starting materials, and its physicochemical properties were investigated using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) spectroscopy, scanning electron microscopy (SEM), energy dispersive analysis of X-ray (EDAX), transmission electron microscope (TEM), and electrochemical methods. The sample prepared displays a monoclinic structure with a space group of P2₁/n, and its surface is covered with a rough and porous carbon layer. In the voltage range of 3.0-4.3 V, the Li₃V₂(PO₄)₃ electrode displays a large reversible capacity, good rate capability and excellent cyclic stability at both 25 and 55 °C. The largest reversible capacity of 130 mAh g⁻¹ was obtained at 0.1C and 55 °C, nearly equivalent to the reversible cycling of two lithium ions per Li₃V₂(PO₄)₃ formula unit (133 mAh g⁻¹). It was found that the increase in total carbon content can improve the discharge performance of the Li₃V₂(PO₄)₃ electrode. In the voltage range of 3.0-4.8 V, the extraction and reinsertion of the third lithium ion in the carbon coated Li₃V₂(PO₄)₃ host are almost reversible, exhibiting a reversible capacity of 177 mAh g⁻¹ and good cyclic performance. The reasons for the excellent electrochemical performance of the carbon coated Li₃V₂(PO₄)₃ cathode material were also discussed.     

Long-term cyclability and high-rate capability of Li3V2(PO4)3/C cathode material using PVA as carbon source

The Li₃V₂(PO₄)₃/C composite cathode material is synthesized via a simple carbothermal reduction reaction route using polyvinyl alcohol (PVA) as both reduction agent and carbon source. The XRD pattern shows that the as-prepared Li₃V₂(PO₄)₃/C composite has a monoclinic structure with space group P2₁/n. The result of XPS shows the oxidation state of V in the Li₃V₂(PO₄)₃/C composite is +3. The Raman spectrum reveals that the coating carbon has a good structure with a low I_D/I_G ratio. The high-quality carbon can not only enhance the electronic conductivity of the Li₃V₂(PO₄)₃/C composite but also prevent the growth of the particle size. The electrochemical performance, which is especially notable for its high-rate performance, is excellent. It delivers an initial discharge capacity of 105.3 mAh/g at 5 C, which is retained as high as 90% after 2000 cycles. No capacity loss can be observed up to 300 cycles under 20 C rate condition. Our experimental results suggest that this compound can be a candidate as cathode materials for the power batteries of hybrid electric vehicles (HEVs) and electric vehicles (EVs) in the future.     

Fabrication and photocatalytic performance of one-dimensional Ag3PO4 sensitized SrTiO3 nanowire

The 1D Ag₃PO₄ sensitized SrTiO₃ nanowires are prepared by simple route of electrospinning-in situ deposition technique. The results of the thermogravimetry (TG), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive Spectrometer (EDS), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and UV–Visible diffuse reflectance spectroscopy (UV–Vis) indicate that the Ag₃PO₄ nanoparticles has been deposited on the surface of the SrTiO₃ nanowires successfully. Experimental results showed that compared with pure SrTiO₃, the as-prepared 1D Ag₃PO₄ sensitized SrTiO₃ nanowires exhibit obvious enhancement of photocatalytic performance and stability. Especially, the Ag₃PO₄/SrTiO₃ (3AS sample) had a satisfactory photocatalytic activity for degrading methylene blue (MB) more than 98% under visible light irradiation. As to pure SrTiO₃ and Ag₃PO₄, only 9.8% and 49% of MB was decomposed after 35?min irradiation respectively. Furthermore, the mechanism of the enhancing photocatalytic activity could be ascribed to the nano-heterojunction of the Ag₃PO₄/SrTiO₃, the visible light response of the Ag₃PO₄, and the 1D structure of the nanowires.     

Electrochemical performance of Li3V2(PO4)3/C cathode material using a novel carbon source

Polyethylene glycol (PEG, mean molecular weight of 10,000) has been used to prepare a Li₃V₂(PO₄)₃/C cathode material by a simple solid-state reaction. The Raman spectra shows that the coating carbon has a good structure with a low I_D/I_G ratio. The images of SEM and TEM show that the carbon is dispersed between the Li₃V₂(PO₄)₃ particles, which improves the electrical contact between the corresponding particles. The electronic conductivity of Li₃V₂(PO₄)₃/C composite is 7.0 × 10⁻¹ S/cm, increased by seven orders of magnitude compared with the pristine Li₃V₂(PO₄)₃ (2.3 × 10⁻⁸ S/cm). At a low discharge rate of 0.28C, the sample presents a high discharge capacity of 131.2 mAh/g, almost achieving the theoretical capacity (132 mAh/g) for the reversible cycling of two lithium. After 500 cycles, the discharge capacity is 123.9 mAh/g with only 5.6% fading of the initial specific capacity. The Li₃V₂(PO₄)₃/C material also exhibits an excellent rate capability with high discharge capacities of 115.2 mAh/g at 1C and 106.4 mAh/g at 5C.     

Study on synthesis routes and their influences on chemical and electrochemical performances of Li3V2(PO4)3/carbon

In this study, Li₃V₂(PO₄)₃/carbon samples were synthesized by two different synthesis routes. Their influence on chemical and electrochemical performances of Li₃V₂(PO₄)₃/carbon as cathode materials for lithium-ion batteries was investigated. The structure and morphology of Li₃V₂(PO₄)₃/carbon were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscope (TEM) measurements. TEM revealed that the Li₃V₂(PO₄)₃ grains synthesized through the sol-gel route had a depressed grain size. Electrochemical behaviors were characterized by galvanostatic charge/discharge, cyclic voltammetry and AC impedance measurements. Li₃V₂(PO₄)₃/carbon with smaller grain size showed better performances in terms of the discharge capacity and cycle stability. The improved electrochemical properties of the Li₃V₂(PO₄)₃/carbon were attributed to the depressed grain size and enhanced electrical contacts produced via the sol-gel route. AC impedance measurements also showed that the sol-gel route significantly decreased the charge-transfer resistance and shortened the migration distance of lithium ion.     

Electrochemical properties of TiP2O7 and LiTi2(PO4)3 as anode material for lithium ion battery with aqueous solution electrolyte

Some polyanionic compounds, e.g. TiP₂O₇ and LiTi₂(PO₄)₃ with 3D framework structure were proposed to be used as anodes of lithium ion battery with aqueous electrolyte. The cyclic voltammetry properties TiP₂O₇ and LiTi₂(PO₄)₃ suggested that Li-ion de/intercalation reaction can occur without serious hydrogen evolution in 5 M LiNO₃ aqueous solution. The TiP₂O₇ and LiTi₂(PO₄)₃ give capacities of about 80 mAh/g between potentials of −0.50 V and 0 V (versus SHE) and 90 mAh/g between −0.65 V and −0.10 V (versus SHE), respectively. A test cell consisting of TiP₂O₇/5 M LiNO₃/LiMn₂O₄ delivers approximately 42 mAh/g (weight of cathode and anode) at average voltage of 1.40 V, and LiTi₂(PO₄)₃/5 M LiNO₃/LiMn₂O₄ delivers approximately 45 mAh/g at average voltage of 1.50 V. Both as-assembled cells suffered from short cycle life. The capacity fading may be related to deterioration of anode material.     

Preparation and electrochemical performance studies on Cr-doped Li3V2(PO4)3 as cathode materials for lithium-ion batteries

Cr-doped Li₃V_2−xCr_x(PO₄)₃/C (x = 0, 0.05, 0.1, 0.2, 0.5, 1) compounds have been prepared using sol–gel method. The Rietveld refinement results indicate that single-phase Li₃V_2−xCr_x(PO₄)₃/C with monoclinic structure can be obtained. Although the initial specific capacity decreased with Cr content at a lower current rate, both cycle performance and rate capability have excited improvement with moderate Cr-doping content in Li₃V_2−xCr_x(PO₄)₃/C. Li₃V_1.9Cr_0.1(PO₄)₃/C compound presents an initial capacity of 171.4 mAh g⁻¹ and 78.6% capacity retention after 100 cycles at 0.2C rate. At 4C rate, the Li₃V_1.9Cr_0.1(PO₄)₃/C can give an initial capacity of 130.2 mAh g⁻¹ and 10.8% capacity loss after 100 cycles where the Li₃V₂(PO₄)₃/C presents the initial capacity of 127.4 mAh g⁻¹ and capacity loss of 14.9%. Enhanced rate and cyclic capability may be attributed to the optimizing particle size, carbon coating quality, and structural stability during the proper amount of Cr-doping (x = 0.1) in V sites.     

Hydrothermal synthesis and rate capacity studies of Li3V2(PO4)3 nanorods as cathode material for lithium-ion batteries

It is an effective method by synthesizing one-dimensional nanostructure to improve the rate performances of cathode materials for Li-ion batteries. In this paper, Li₃V₂(PO₄)₃ nanorods were successfully prepared by hydrothermal reaction method. The structure, composition and shape of the prepared were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scan electron microscope (SEM) and transmission electron microscope (TEM), respectively. The data indicate the as-synthesis powders are defect-rich nanorods and the sizes are the length of several hundreds of nanometers to 1 μm and the diameter of about 60 nm. The preferential growth direction of the prepared material was the [1 2 0]. The electrodes consisting of the Li₃V₂(PO₄)₃ nanorods show the better discharge capacities at high rates over a potential range of 3.0-4.6 V. These results can be attributed to the shorter distance of electron transport and the fact that ion diffusion in the electrode material is limited by the nanorod radius. All these results indicate that the resulting Li₃V₂(PO₄)₃ nanorods are promising cathode materials in lithium-ion batteries.     

A novel LiTi2(PO4)3/MnO2 hybrid supercapacitor in lithium sulfate aqueous electrolyte

In this work, carbon-coated lithium-ion intercalated compound LiTi₂(PO₄)₃ and MnO₂ have been synthesized and they deliver a capacity of 90 and 60 mAh/g in 1 M Li₂SO₄ neutral aqueous electrolyte within safe potentials without O₂ and H₂ evolution, respectively. The novel hybrid supercapacitor in which MnO₂ was used as a positive electrode and carbon-coated LiTi₂(PO₄)₃ as a negative electrode was assembled and the LiTi₂(PO₄)₃/MnO₂ hybrid supercapacitor showed a sloping voltage profile from 0.7 to 1.9 V, at an average voltage near 1.3 V, and delivers a capacity of 36 mAh/g and an energy density of 47 Wh/kg based on the total weight of the active electrode materials. It exhibits a desirable profile and maintains over 80% of its initial energy density after 1000 cycles. The hybrid supercapacitor also exhibit an excellent rate capability, even at a power density of 1000 W/kg, it has a specific energy 25 Wh/kg compared with 43 Wh/kg at the power density about 200 W/kg.