Magnetic recyclable ZnO/SrFe12O19 photocatalyst for effective photodegradation of rhodamine B under simulated sunlight

This work develops a novel magnetic photocatalysts ZnO/SrFe₁₂O₁₉ (ZS) synthesized with hydrothermal process. The introduction of SrFe₁₂O₁₉ not only enhances the photocatalytic behavior of ZnO towards Rhodamine B (RhB) decomposition, but also reinforces the recycling stability. Especially, ZS-5 composite exhibits the optimal photocatalytic performance, and the RhB decomposition reaches 99.5% after being exposed to simulative sunlight for 70 min, which is obviously superior to that of bare ZnO. Furthermore, the ZS-5 can be recovered from RhB solution by an extra magnet space and reused. After five recycles, the RhB removal efficiency can still be maintained over 90%. Such prominent photocatalytic property and stability of ZS-5 are associated with the greatly improved detachment efficiency of photoexcited carriers in a magnetic field. This study could provide a new-type recyclable photocatalyst that can effectively purify dye wastewater for convenient recovery.     

Magnetic properties,phase evolution,hollow structure and biomedical application of hematite (α-Fe2O3) and QUAIPH

We investigate synthesis, phase evolution, hollow and porous structure and magnetic properties of quasi-amorphous intermediate phase (QUAIPH) and hematite (α-Fe₂O₃) nanostructure synthesized by annealing of akaganeite (β-FeOOH) nanorods. It is found that the annealing temperature determines the phase composition of the products, the crystal structure/size dictates the magnetic properties whereas the final nanorod morphology is determined by the starting material. Annealing of β-FeOOH at ～300 °C resulted in the formation of hollow QUAIPH nanorods. The synthesized material shows low-cytotoxicity, superparamagnetism and good transverse relaxivity, which is rarely reported for QUAIPH. The QUAIPH nanorods started to transform to porous hematite nanostructures at ～350 °C and phase transformation was completed at 600 °C. During the annealing, the crystal structure changed from monoclinic (akaganeite) to quasi-amorphous and rhombohedral (hematite). Unusually, the crystallite size first decreased (akaganeite → QUAIPH) and then increased (QUAIPH → hematite) during annealing whereas the nanorods retained particle shape. The magnetic properties of the samples changed from antiferromagnetic (akaganeite) to superparamagnetic with blocking temperature T_B = 84 K (QUAIPH) and finally to weak-ferromagnetic with the Morin transition at T_M = 244 K and high coercivity H_C = 1652 Oe (hematite). The low-cytotoxicity and MRI relaxivity (r₂ = 5.80 mM^?1 s^?1 (akaganeite), r₂ = 4.31 mM^?1 s^?1 (QUAIPH) and r₂ = 5.17 mM^?1 s^?1 (hematite)) reveal potential for biomedical applications.     

Pristine and cobalt doped copper sulfide microsphere particles for seawater splitting

In this work, copper sulfide particles are synthesized with different Co doping concentrations such as 0, 1 and 5% at 80 °C by optimizing synthesis times from 1 to 3 h. Copper sulfide particles possess two structural phases of covellite CuS and digenite Cu₉S₅. The increase in synthesis time from 1 to 3 h increases the Cu₉S₅ phase growth and changes the morphology from flower to microsphere. The CuS synthesized with 0, 1 and 5% Co dopant concentrations demonstrate flower consisting of agglomerated nanosheets, microsphere and flower like microsphere. The elemental investigation substantiates Co ions presence in CuS microspheres. The A_1g (LO) mode intensity is decreased with increase in Co dopant concentration confirming Co incorporation into CuS microsphere. The CuS synthesized with 0, 1, 5% Co dopants exhibit 322 mV, 305 mV and 289 mV to attain 100 mA/cm² in 1 M KOH seawater. The CuS synthesized with 5% Co dopant demonstrates higher double layer capacitance (C_dl) of 173.9 mFcm^?2 and lower charge transfer resistance (R_ct) of 6.07 Ω with 78.84% retention after 10 h continuous stability than that of the other pristine (118.3 mFcm^?2, 13.72 Ω) and 1% Co doped CuS microsphere (165.7 mFcm^?2, 8.55 Ω) indicating more surface active site and rapid charge carrier transport, respectively.     

A dotted nanowire arrayed by 5 nm sized palladium and nickel composite nanopaticles showing significant electrocatalytic activity towards ethanol oxidation reaction (EOR)

To the best of our knowledge, this is the first time to report the preparation of a dotted nanowire arrayed by 5 nm sized palladium and nickel composite nanoparticles (denoted as Pd_xNi_y NPs) via a hydrothermal method using NU and PdO·H₂O as the starting materials. The samples prepared at the mass ratio of NU to PdO·H₂O 1:1, 1:2 and 2:1 were, respectively, nominated as catalyst c₁, c₂ and c₃. The chemical compositions of all synthesized catalysts were mainly studied by using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), revealing that metallic Ni was one main component of all prepared catalysts. Surprisingly, the main diffraction peaks appearing in the XRD patterns of all prepared catalysts were assigned to the metallic Ni rather than the metallic Pd. Very interestingly, as indicated by the TEM images, a large number of dotted nanowires arrayed by numerous equidistant 5 nm sized nanoparticles were distinctly exhibited in catalyst c₁. More importantly, when being used as electrocatalysts for EOR, all prepared catalysts exhibited an evident electrocatalytic activity towards EOR. In the cyclic voltammetry (CV) test, the peak current density of the forward peak of EOR on catalyst c₁ measured at 50 mV s^?1 was as high as 56.1 mA cm^?2, being almost 9 times higher than that of EOR on catalyst c₃ (6.3 mA cm^?2). Particularly, the polarized current density of EOR on catalyst c₁ at 3600 s, as indicated by the chronoamperometry (CA) experiment, was still maintained to be around 1.47 mA cm^?2, a value higher than the latest reported data of 1.3 mA cm^?2 (measured on the pure Pd/C electrode). Presenting a novel method to prepare dotted nanowires arranged by 5 nm sized nanoparticles and showing the significant eletrocatalytic activities of the newly prepared dotted nanowires towards EOR were the major contributions of this preliminary work.     

High performance asymmetric supercapacitor based on 3D microsphere-like 1T-MoS2 with high 1T phase content

1T phase molybdenum disulfide (1T-MoS₂) has aroused extensive concern in energy storage devices such as supercapacitors due to its large interlayer spacing, high conductivity and good hydrophilicity. However, it is struggle to synthesize 1T-MoS₂ with stable 1T phase with high content. Herein, Ammonium ion intercalation molybdenum disulfide (A-MoS₂) with high 1T content and stable 3D microsphere structure was successfully synthesized using a facile hydrothermal method. We explained the feasibility of ammonium ion (NH₄⁺) intercalation through density functional theory (DFT) calculations and proved the successful intercalation of NH₄⁺ by XRD and XPS. Through XPS fitting, the 1T phase content is calculated as high as 83.1%. The as-prepared A-MoS₂ presents a stable 3D microsphere structure with the interlayer spacing expanded to 0.93 nm, which provides a wide ion diffusion channel that allows ions to pass through quickly. Moreover, the high 1T content increases the hydrophilicity of MoS₂, thereby improving the wettability of the electrode, which contributes to the interaction between the electrolyte and electrode. In 1 M Na₂SO₄, A-MoS₂ electrode material displays high specific capacitance of 228 F g^?1 at 5 mV s^?1 and retains 127 F g^?1 at 80 mV s^?1, which proves the good rate capability. Furthermore, the assembled α-MnO₂//A-MoS₂ asymmetric supercapacitor (ASC) displayed a wide operating voltage of 2.1 V. The assembled ASC displays a high energy density of 35.8 Wh?kg^?1 at a power density of 525.0 W kg^?1, which indicates excellent energy storage performance.     

Nitrogen-doped cobalt sulfide as an efficient electrocatalyst for hydrogen evolution reaction in alkaline and acidic media

The enhancement in intrinsic catalytic activity and material conductivity of an electrocatalyst can leads to promoting HER activity. Herein, a successful nitrogenation of CoS₂ (N–CoS₂) catalyst has been investigated through the facile hydrothermal process followed by N₂ annealing treatment. An optimized N–CoS₂ catalyst reveals an outstanding hydrogen evolution reaction (HER) performance in alkaline as well as acidic electrolyte media, exhibiting an infinitesimal overpotential of ?0.137 and ?0.097 V at a current density of ?10 mA/cm² (?0.309 and ?0.275 V at ?300 mA/cm²), corresponding respectively, with a modest Tafel slope of 117 and 101 mV/dec. Moreover, a static voltage response was observed at low and high current rates (?10 to ?100 mA/cm²) along with an excellent endurance up to 50 h even at ?100 mA/cm². The excellent catalytic HER performance is ascribed to improved electronic conductivity and enhanced electrochemically active sites, which is aroused from the synergy and mutual interaction between heteroatoms that might have varied the surface chemistry of an active catalyst.     

Synthesis of manganese titanate and its precursors from xerogel

An overview of research on the synthesis of manganese titanates is presented. The xerogel of Mn–Ti–O–C–H composition was synthesized from manganese acetate and titanium tetrabutylate via liquid-phase method using organic solvents. The calcination of xerogel in air at 450 °C and 700 °C yielded manganese titanate precursors in the form of a nanostructured mixture of Mn₂O₃ and TiO₂. Annealing at 1000 °C, manganese metatitanate MnTiO₃ was obtained. Reference experiments with initial reagents included, separately, thermal decomposition of Mn(CH₃COO)₂×4H₂O and the product of Ti(OC₄H₉)₄ hydrolysis. The composition, structure, and properties of the products were studied using X-ray diffraction, scanning electron microscopy, elemental analysis, diffuse reflectance IR Fourier spectroscopy, thermogravimetry, and by measuring specific surface area. The data presented by these different techniques are basically consistent with each other (with an increase in the annealing temperature, an increase in globule size and decrease in specific surface area are observed; structuring occurs within the long- and short-range order; the size of the crystallites does not exceed that of the globules; elemental composition correlates with phase composition; the endothermic character of the reaction of MnTiO₃ formation at 900 °C is confirmed by a thermodynamic calculation). Nevertheless, some unexpected effects were revealed (based on the FTIR diffuse reflection spectra, mixed oxide Mn–Ti–O is formed in the surface layer of particles already at 450 °C and 700 °C; etc.). Application of the proposed technique for modifying Al₂O₃ powders, with the aim of implementing low-temperature sintering of corundum ceramics, is discussed.     

Fluoride-mediately solvothermal synthesis and tunable photocatalytic selectivity of urchin-like ZrO2 hollow microspheres

Photocatalysts often show excellent performances on the basis of their surface state of exposed faces with high reactivity, but unfortunately surfaces of this type are usually concealed into the interior of crystals for their high surface energy. We report here a possibility that for fluorine-terminated surfaces of monoclinic ZrO₂, these higher-energy surfaces could be retained and exposed. Urchin-like ZrO₂ hollow microspheres (UZHS) composed of nanoribbons with exposed (010) facets are obtained through a fluoride mediately solvothermal method. We prove the stabilization effect of fluorine adsorption on (010) facets by density functional theory calculations. More interestingly, UZHS exhibit tunable photocatalytic selectivity in dye degradation. The fluorinated UZHS exhibit good performances both on decomposing Congo red (CR) and methylene blue, while the surface-modified UZHS by calcination only favor decomposition of CR.     

Different hydrothermal corrosion results between two sides of sodalime float glass and the possible corrosion mechanism

Sodalime float (SF) glass is widely used in our societies and industries. Hydrothermal corrosion method is one of the effective ways to prepare a superhydrophobic glass, but there is still lack of knowledge about hydrothermal corrosion behavior and mechanism of SF glass. We have hydrothermally treated SF glass at 180 °C for different time, and tried to reveal the aqueous corrosion process of SF glass. We have characterized the morphologies and chemical compositions of samples, and found that (1) the two sides of SF glass have different corrosion resistances, and (2) a multilayer structural coating with a nanoflake layer (Mg-rich gel layer), a nanowire layer (Ca-rich gel layer), and a porous layer (etched layer) is formed on the air-side of SF glass. Based on the experimental results, we have proposed an aqueous corrosion mechanism of SF glass. The insights of the hydrothermal corrosion behaviors and mechanism provide helpful guidelines to glass surface structural control and functionalization.     

Morphological evolution on the surface of hydrothermally synthesized hydroxyapatite microspheres in the presence of EDTMP

Well-ordered and surface engineered hierarchical hydroxyapatite microspheres (HAM) were prepared via a template free hydrothermal process. Ethylene diamine tetra (methylene phosphonic acid) (EDTMP) was used as chelating or regulating agent for the first time in this study. The results indicated the formation of sheet-like particles in the absence of EDTMP. On the other hand, microspheres with radially grown nanorods (HAMNR) or nanosheets (HAMNS) on the surface were obtained (with average diameter of 5?µm) in the presence of EDTMP. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy were used to characterize the crystalline phases in the synthesized samples. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed that EDTMP concentration played an important part in regulating the morphology to form well organized microspheres with nanosheets or nanorods on the surface. Brunauer-Emmett-Teller (BET) revealed an increase in the specific surface area with the change in morphology from the HAMNS to HAMNR. Possible mechanisms are proposed to account for the formation of different morphologies based upon thermodynamic and kinetic theories.