Cobalt-aluminum spinel supported on modified γ-alumina for peroxymonosulfate activation: Si-Al ratio of support to optimize performance and reusability.

The development of cobalt-based supported catalysts with high PMS catalytic activity and stability by adjusting the composition of the support is highly desirable yet remains scarce. In the work, a series of catalysts (Co2AlO4/Al2O3-xSiO2) were prepared by impregnation and high-temperature calcination using Al2O3-xSiO2 with a low Si-Al ratio as the support. Measurement techniques such as XRD, XPS, UV-DRS, FTIR, BET, SEM and HRTEM were used to characterize textural and chemical properties (ratio of Co3+/Co2+, specific surface area, pore size, pore volume, etc.). The ratio of Co3+/Co2+ and pore volume of Co2AlO4/Al2O3-xSiO2 can be turned by controlling the ratio of Si to Al, which are closely related to the catalytic performance and reusability of the catalysts. The optimized catalyst (Co2AlO4/Al2O3-0.25SiO2) can completely degrade 10 mg/L p-nitrophenol (PNP) in 40 min in the pH range of 3-9 with excellent reusability. The effects of several reaction parameters (i.e., PMS dosage, Co2AlO4/Al2O3-0.25SiO2 dosage, reaction temperature, initial pH value, and inorganic ions) on PNP removal were comprehensively investigated. Sulfate radical (SO4•-) and singlet oxygen (1O2) are making a major contribution to the degradation of PNP. Moreover, a millimeter-scale catalyst (CoSiAl-0.25/Al2O3 pellet) was prepared by sol adsorption and high-temperature calcination method, which maintained high oxidation activity after treatment of 18 L wastewater (PNP of 10 mg/L) in a continuous flow process. The method is simple and easy to operate on a large scale, providing a new perspective on the design and preparation of cobalt-aluminum spinel catalysts for activated PMS.

Long-acting CoAl2O4 spinel catalyst developed on activated alumina pellets by facile synthesis to activate peroxymonosulfate: Controllable cobalt leaching and environmental adaptability.

A novel composite catalyst prepared by fixing cobalt aluminate (CoAl2O4) spinel on formed alumina carrier by impregnation-calcination route is reported, which can be used to efficiently activate peroxymonosulfate (PMS) to degrade p-nitrophenol (PNP). The internal laws of phase composition and preparation conditions are explored in detail, and the results show that the introduction of additional aluminum ions in the preparation process changes the coordination environment and the electronic state of cobalt ions, which leads to the transformation of spinel/inverted spinel in the composition, and further affects the activity and stability of the catalyst. The selected CoAl-Aaps-600 catalyst has high CoAl2O4 content, showing good cycle performance and low cobalt leaching, and has great catalytic degradation performance at different temperatures and a wide pH range. Most notably, a fixed bed reactor packed with 20 g of CoAl-Aaps-600 exhibits excellent capacity to continuously treat 60 L of PNP solution with acceptable PNP removal ratio and low cobalt leaching content. Sulfate radical and singlet oxygen are identified as the main reactive oxygen species produced in CoAl-Aaps-600/PMS system, and the reaction mechanism is reasonably inferred. This work provides a potential application material and process for the treatment of continuous organic wastewater.

Fabrication of novel sandwich nanocomposite as an efficient and regenerable adsorbent for methylene blue and Pb (II) ion removal.

An adsorbent, which is easy to be separated and reused after adsorption, is very important for the removal of pollutants in aqueous solution. Hence, a novel nanofibrous sandwich structured adsorbent of silica nanofiber/magnetite nanoparticles/porous silica (SNF/MNP/PS) was designed and synthesized for the first time. The magnetite nanoparticles with diameter less than 10 nm were evenly distributed on the surface of silica nanofiber, which was subsequently fully covered by a layer of porous silica. The novel adsorbent was proved possessing good adsorption capacity for both methylene blue (MB) and Pb (II) ion (Pb2+), and the adsorption equilibrium could be well described by the Langmuir-isotherm model with the maximum adsorption capacity of 103.1 mg/g for MB and 243.9 mg/g for Pb2+ at 288 K. Moreover, in MB-Pb2+ mixed system the measured adsorption capacity reached 74.5 mg/g for MB and 202.4 mg/g for Pb2+, respectively. The saturated adsorbent could be readily magnetically separated from the solution and then efficiently regenerated by heterogeneous Fenton-like reaction (for MB) or acidic desorption process (for Pb2+), respectively. After 5 cycles of adsorption-regeneration, the adsorption capacity of the reused adsorbent still reached 81.0% (for MB) and 70.9% (for Pb2+) of the initial value. The SNF/MNP/PS behaves good adsorption properties for different types of pollutants, high magnetic recoverability and regeneration efficiency, which make it applicable to different contaminants removal.

Carbon sphere@Co9S8 yolk-shell structure with good morphology stability for improved lithium storage performance.

The poor electronic conductivity and huge volume expansion of cobalt sulfides upon cycling would lead to their poor electrochemical performances for Lithium-ion batteries. Here, we rationally design a yolk-shell carbon sphere@Co9S8 (C@CS) composite, which demonstrates improved kinetics and excellent morphology stability during cycling. This structure can keep Co9S8 shell from collapse and aggregation. After cycling, a layer of thin solid electrolyte interphase is coated on the Co9S8 shells and prevented them from dissolving in electrolyte, which is helpful for the electrochemical performances. As a result, the C@CS electrodes exhibit good lithium storage performances, including excellent cyclic stability up to 300 cycles at 1000 and 2000 mA g-1 and high-rate property of 4000 mA g-1 with a capacity of 489 mA h g-1.

Highly efficient fluoride adsorption from aqueous solution by nepheline prepared from kaolinite through alkali-hydrothermal process.

A direct alkali-hydrothermal induced transformation process was adopted to prepare nepheline from raw kaolinite (shortened form RK in this paper) and NaOH solution in this paper. Structure and morphology characterizations of the synthetic product showed that the nepheline possessed high degree of crystallinity and uniform surface morphology. Specific surface area of nepheline is 18 m2/g, with a point of zero charge at around pH 5.0-5.5. The fluoride (F- ions) adsorption by the synthetic nepheline (shortened form SN in this paper) from aqueous solution was also investigated under different experimental conditions. The adsorption process well matched the Langmuir isotherm model with an amazing maximum adsorption capacity of 183 mg/g at 323 K. The thermodynamic parameters (ΔG0, ΔH0, and ΔS0) for adsorption on SN were also determined from the temperature dependence. The adsorption capacities of fluoride on SN increased with increasing of temperature and initial concentration. Initial pH value also had influence on adsorption process. Adsorption of fluoride was rapidly increased in 5-60 min and thereafter increased slowly to reach the equilibrium in about 90-180 min under all conditions. The adsorption followed a pseudo-second order rate law.

BiOCl/TiO2/diatomite composites with enhanced visible-light photocatalytic activity for the degradation of rhodamine B.

A BiOCl/TiO2/diatomite (BTD) composite was synthesized via a modified sol-gel method and precipitation/calcination method for application as a photocatalyst and shows promise for degradation of organic pollutants in wastewater upon visible-light irradiation. In the composite, diatomite was used as a carrier to support a layer of titanium dioxide (TiO2) nanoparticles and bismuth oxychloride (BiOCl) nanosheets. The results show that TiO2 nanoparticles and BiOCl nanosheets uniformly cover the surface of diatomite and bring TiO2 and BiOCl into close proximity. Rhodamine B was used as the target degradation product and visible light (λ > 400 nm) was used as the light source for the evaluation of the photocatalytic properties of the prepared BTD composite. The results show that the catalytic performance of the BTD composite under visible-light irradiation is much higher than that of TiO2 or BiOCl alone. When the molar ratio of BiOCl to TiO2 is 1:1 and the calcination temperature is 400 °C, the composite was found to exhibit the best catalytic effect. Through the study of the photocatalytic mechanism, it is shown that the strong visible-light photocatalytic activity of the BTD composite results mainly from the quick migration of photoelectrons from the conduction band of TiO2/diatomite to the surface of BiOCl, which promotes the separation effect and reduces the recombination rate of the photoelectron-hole pair. Due to the excellent catalytic performance, the BTD composite shows great potential for wide application in the field of sewage treatment driven by solar energy.

Metal organic frameworks derived cobalt sulfide/reduced graphene oxide composites with fast reaction kinetic and excellent structural stability for sodium storage.

We report a metal-organic framework-derived Co9S8 nanoflakes on reduced graphene oxide sheet composites as an advanced sodium-ion battery anode. Using a galvanostatic intermittent titration technique, we reveal that the sodium diffusion coefficient of the composite is higher than that of its counterpart. Ex-situ scanning electron microscopy images suggest the excellent mechanical stability of Co9S8 nanoflakes on the reduced graphene oxide sheet electrode during cycling, thereby facilitating cyclic stability. The partial surface-induced capacitive effect also contributes to electrochemical performance. With the reduced graphene oxide, the Co9S8 nanoflakes on the reduced graphene oxide sheet electrode deliver a high discharge capacity of 551 mA h g-1 at 0.1 A g-1, a good rate capability at 10 A g-1, and an excellent cyclic stability up to 500 cycles. rGO/Co9S8 shows potential for practical applications in Na3V2(PO4)3‖rGO/Co9S8 full cells.

Carbon-coated cobalt oxide porous spheres with improved kinetics and good structural stability for long-life lithium-ion batteries.

Current anode materials for lithium-ion batteries (LIBs) mainly suffer from poor electronic conductivity and large volume expansion upon cycling. Improving kinetics and designing good morphology structural stability of electrode materials can effectively enhance the lithium storage performances of LIBs. In this study, we successfully synthesized hierarchical carbon-coated cobalt oxide (C@CoO) porous spheres with improved kinetics and good structural stability, which were investigated by ex situ electrochemical impedance spectrometry, scanning electron microscopy, and powder X-ray diffraction. We also optimized the preparation conditions of the C@CoO porous spheres. The C@CoO350 porous spheres exhibited good electrochemical performances including the high 2nd specific capacity of 811mAhg-1 at 0.1Ag-1 and good rate property of 450mAhg-1 at 4Ag-1. Furthermore, it demonstrated an excellent cyclic stability with a high capacities of 669mAhg-1 after 400 cycles at 0.5Ag-1. Results demonstrated that C@CoO350 porous spheres are promising LIBs anodes.

Synthesis of a MnO2/Fe3O4/diatomite nanocomposite as an efficient heterogeneous Fenton-like catalyst for methylene blue degradation.

Heterogeneous Fenton-like catalysts with the activation of peroxymonosulfate (PMS), which offer the advantages of fast reaction rate, wide functional pH range and cost efficiency, have attracted great interest in wastewater treatment. In this study, a novel magnetic MnO2/Fe3O4/diatomite nanocomposite is synthesized and then used as heterogeneous Fenton-like catalyst to degrade the organic pollutant methylene blue (MB) with the activation of PMS. The characterization results show that the Fe3O4 nanoparticles and nanoflower-like MnO2 are evenly distributed layer-by-layer on the surface of diatomite, which can be readily magnetically separated from the solution. The as-prepared catalyst, compared with other Fenton-like catalysts, shows a superb MB degradation rate of nearly 100% in 45 min in the pH range of 4 to 8 and temperature range of 25 to 55 °C. Moreover, the nanocomposite shows a good mineralization rate of about 60% in 60 min and great recyclability with a recycle efficiency of 86.78% after five runs for MB. The probable mechanism of this catalytic system is also proposed as a synergistic effect between MnO2 and Fe3O4.

Degradation and Mineralization of Benzohydroxamic Acid by Synthesized Mesoporous La/TiO2.

Rare earth element La-doped TiO2 (La/TiO2) was synthesized by the sol-gel method. Benzohydroxamic acid was used as the objective pollutant to investigate the photocatalytic activity of La/TiO2. The physicochemical properties of the prepared materials were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, UV-vis diffuse reflectance spectroscopy, specific surface area and porosity, scanning electron microscopy and transmission electron microscopy. As a result, the doping of La could inhibit the crystal growth of TiO2, increase its specific surface area and expand its response to visible light, thus improving its photocatalytic activity. La/TiO2 with the doping ratio of 0.75% calcined at 500 °C, showing the highest photocatalytic activity to degrade benzohydroxamic acid under the irradiation of 300 W mercury lamp. About 94.1% of benzohydroxamic acid with the original concentration at 30 mg·L-1 was removed after 120 min in a solution of pH 4.4 with an La/TiO2 amount of 0.5 g·L-1. Furthermore, 88.5% of the total organic carbon was eliminated after 120 min irradiation. In addition, after four recycling runs, La/TiO2 still kept high photocatalytic activity on the photodegradation of benzohydroxamic acid. The interfacial charge transfer processes were also hypothesized.