Efficient degradation of ciprofloxacin in wastewater by CuFe2O4/CuS photocatalyst activated peroxynomosulfate.

In this study, CuFe2O4/CuS composite photocatalysts were successfully synthesized for the activation of peroxynomosulfate to remove ciprofloxacin from wastewater. The structural composition and morphology of the materials were analyzed by XRD, SEM, TEM, and Raman spectroscopy. The electrochemical properties of the samples were tested by an electrochemical workstation. The band gap of the samples was calculated by DFT and compared with the experimental values. The effects of different catalysts, oxidant PMS concentrations, and coexisting ions on the experiments were investigated. The reusability and stability of the photocatalysts were also investigated. The mechanism of the photocatalytic degradation process was proposed based on the free radical trapping experiment. The results show that the p-p heterojunction formed between the two contact surfaces of the CuFe2O4 nanoparticle and CuS promoted the charge transfer between the interfaces and inhibited the recombination of electrons and holes. CuFe2O4-5/CuS photocatalyst has the best catalytic activity, and the removal rate of ciprofloxacin is 93.7%. The intermediates in the degradation process were tested by liquid chromatography-mass spectrometry (LC-MS), and the molecular structure characteristics of ciprofloxacin were analyzed by combining with DFT calculations. The possible degradation pathways of pollutants were proposed. This study reveals the great potential of the photocatalyst CuFe2O4/CuS in the activation of PMS for the degradation of ciprofloxacin wastewater.

MnFe2O4/polyaniline/diatomite composite with multiple loss mechanisms towards broadband absorption.

The research and development of absorbing materials with high absorbing capacity, wide effective absorption bandwidth, and lightweight has always been interesting. In this research, a facile hydrothermal method was used to prepare MnFe2O4, and the grain size of MnFe2O4 decreased with increasing hydrothermal temperature. When the size of MnFe2O4 nanoparticles is less than 10 nm, its quantum size effect and surface effect make its electromagnetic microwave absorption performance greatly optimized. When the thickness of MnFe2O4-110 °C is 2.57 mm, the minimum reflection loss (RLmin) is -35.28 dB. Based on this, light porous diatomite and a three-dimensional polyaniline network are introduced. Diatomite is used as the base material to effectively reduce the agglomeration of MnFe2O4 quantum dots. The relatively high surface area introduced by a three-dimensional network of polyaniline promotes the orientation, interfacial polarization, multiple relaxation, and impedance matching, thereby generating further dielectric loss. Additionally, the magnetic properties of manganese ferrite and the strong electrical conductivity of polyaniline play an appropriate complementary role in electromagnetic wave absorption. The RLmin of MnFe2O4/PANI/diatomite is -56.70 dB at 11.12 GHz with an absorber layer thickness of 2.57 mm. The effective frequency bandwidth (RL < -10 dB) ranges from 9.21 to 18.00 GHz. The absorption mechanism indicates that the high absorption intensity is the result of the synergistic effect of impedance matching, conduction losses, polarization losses, and magnetic losses.

Poly(vinylidene Fluoride-Hexafluoropropylene) Porous Membrane with Controllable Structure and Applications in Efficient Oil/Water Separation.

Poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) porous membranes are fabricated via thermally induced phase separation (TIPS) with mixed diluent (dibutyl phthalate (DBP)/dioctyl phthalate (DOP)). The effects of mixed diluent are discussed in detail in term of morphology, mean pore size, selective wettability, etc. The results show that the membrane structure changes from spherulitic to bicontinuous with the change of DBP/DOP ratio. It is also found that the degree of crystallization decreases with the decrease of DBP/DOP ratio in mixed diluent. When liquid-liquid (L-L) phase separation precedes solid-liquid (S-L) phase separation, the obtained membranes have outstanding hydrophobicity and lipophilicity, excellent mechanical property. Additionally, the PVDF-HFP hybrid membranes are prepared with silica (SiO2) particles and the effect of SiO2 content on structure and properties is discussed. It is found that the PVDF-HFP hybrid membrane with 2 wt % SiO2 (M3-S2) has better properties and higher filtration rate and separation efficiency for surfactant-stabilized water-in-oil emulsion separation. Moreover, the membrane M3-S2 also exhibits excellent antifouling performance for long-running.

Novel Ultrafine Fibrous Poly(tetrafluoroethylene) Hollow Fiber Membrane Fabricated by Electrospinning.

Novel poly(tetrafluoroethylene) (PTFE) hollow fiber membranes were successfully fabricated by electrospinning, with ultrafine fibrous PTFE membranes as separation layers, while a porous glassfiber braided tube served as the supporting matrix. During this process, PTFE/poly(vinylalcohol) (PVA) ultrafine fibrous membranes were electrospun while covering the porous glassfiber braided tube; then, the nascent PTFE/PVA hollow fiber membrane was obtained. In the following sintering process, the spinning carrier PVA decomposed; meanwhile, the ultrafine fibrous PTFE membrane shrank inward so as to further integrate with the supporting matrix. Therefore, the ultrafine fibrous PTFE membranes had excellent interface bonding strength with the supporting matrix. Moreover, the obtained ultrafine fibrous PTFE hollow fiber membrane exhibited superior performances in terms of strong hydrophobicity (CA > 140°), high porosity (>70%), and sharp pore size distribution. The comprehensive properties indicated that the ultrafine fibrous PTFE hollow fiber membranes could have potentially useful applications in membrane contactors (MC), especially membrane distillation (MD) in harsh water environments.

A hybrid electric field assisted vacuum membrane distillation method to mitigate membrane fouling.

We proposed a novel method for vacuum membrane distillation (VMD) called Electric Field Assisted Vacuum Membrane Distillation (EVMD) that can be used to mitigate membrane fouling. A biaxial stretching polytetrafluoroethylene (PTFE) membrane was utilized as the base membrane, and multi-walled carbon nanotubes (MWCNTs) or a mixture of MWCNTs/graphene as a conductive substrate. During EVMD, the conductive PTFE membrane acted as the cathode while a stainless-steel wire mesh surrounding the conductive membrane acted as the anode. The effect of the per unit area loading mass (PUALM) of the conductive substrate on the membrane performance were investigated. Results revealed that for a PUALM of 10 g m-2, the PTFE membrane not only exhibited excellent conductivity but also showed a high rate of gas flux. Doping graphene into the MWCNT conductive substrate led to the formation of nano-channels which served to improve the membrane distillation flux and the membrane hydrophobicity. The effects of the electric field strength as well as humic acid (HA) concentration on the antifouling performance during EVMD were also investigated. Results showed that during EVMD, the PTFE conductive membrane exhibited the best antifouling ability using an intermittent electric field with a field strength of 1.0 V cm-1.

Structural and diffusion characterizations of steam-stable mesostructured zeolitic UL-ZSM-5 materials.

A series of mesoporous UL-ZSM-5 materials (Si/Al = 50) with different micro- and mesoporosity as well as crystallinity was prepared following the procedure proposed in one of our recent studies (Trong-On, D.; Kaliaguine, S. Angew. Chem. Int. Ed. 2001, 40, 3248-3251. Trong-On, D.; Kaliaguine, S. U.S. Patent 6,669,924, B1, 2003). These materials have zeolitic structure in the form of nanoparticles intergrown in the walls of the amorphous wormhole-like aluminosilicate mesopores of Al-Meso-50, which was used as a precursor in the synthesis. The structure, crystallinity, and textural properties of the synthesized materials, as well as a reference ZSM-5 zeolite sample, were determined by X-ray diffraction (XRD), transmission electron microscopy (TEM)/scanning electron microscoy (SEM) analyses, Fourier transform infrared spectroscopy (FTIR), 27Al magic angle spinning (MAS) nuclear magnetic resonance (NMR), and nitrogen adsorption/desorption techniques. The acid properties were examined by FTIR of adsorbed pyridine. UL-ZSM-5 materials were shown to be highly hydrothermally stable. The diffusion of two C7 hydrocarbons, i.e., n-heptane and toluene, in four UL-ZSM-5 materials with different microporosities, related acidities, and crystallinities were investigated using the zero-length column (ZLC) method. Furthermore, the wormhole-like mesostructured aluminosilicate precursor (Al-Meso-50) and a reference MFI zeolite sample were also investigated using the same technique. A theoretical model considering a combination of mesopore diffusion (with surface slip in the main channels) with an activated, mainly surface diffusion mechanism in the intrawall biporous structure, was proposed and employed to interpret the experimental ZLC results. A classical Knudsen type of diffusion was replaced by an activated surface slip type of diffusion mechanism in the mesopores. The transport of n-heptane in UL-ZSM-5 materials was found to be mainly controlled by mesopore diffusion in the main-channel structure, while that of toluene was dominated by the intrawall diffusion process. Diffusion activation energies of n-heptane are about 2 times higher in comparison to toluene, which has a larger kinetic diameter. The main mesopore channel structure seems to appreciably contribute to the overall mass transport. Furthermore, the effect of hydrothermal treatment (20% steam at 800 degrees C for 24 h) on the diffusion of these two sorbates on UL-ZSM-5 materials was also evaluated.

CO2 dynamic adsorption/desorption on zeolite 5A studied by 13C magnetic resonance imaging.

We present the first 13C magnetic resonance imaging study of CO2 transient adsorption/desorption processes in a zeolite 5A column. CO2 transient concentration profiles were measured with a centric scan spin-echo single point imaging technique. The adsorption wave profiles were determined under flow conditions, with the results analyzed by the Bohart-Adams model. The model adequately accounts for the spatial and the temporal behavior of CO2 in the column. CO2 adsorption rate constants were calculated from the fit. Desorption profiles were acquired by blowing a helium stream through a zeolite 5A column saturated with CO2. An asymmetry between the adsorption and desorption profiles is readily apparent. A linear relationship between the CO2 condensed phase concentration and square root of time was observed.

Adsorption of C7 hydrocarbons on biporous SBA-15 mesoporous silica.

In our recent studies (Vinh-Thang, H.; Huang, Q.; Eic, M.; Trong-On, D.; Kaliaguine, S. Langmuir 2005, 21, 2051-2057; Vinh-Thang, H.; Huang, Q.; Eic, M.; Trong-On, D.; Kaliaguine, S. Stud. Surf. Sci. Catal. 2005, in press), a series of synthesized SBA-15 materials were characterized using nitrogen adsorption/desorption isotherms at 77 K and SEM images. In the present paper, four of them (MMS-1-RT, MMS-1-60, MMS-1-80, and MMS-5-80) were further investigated with regard to their equilibrium characteristics using n-heptane and toluene as sorbates by the standard gravimetric technique. SBA-15 materials proved to have a broad pore size distribution within the micropore/small-mesopore range in the walls of their main mesoporous channels. The adsorption capacities for toluene were found to be higher than for n-heptane. The isosteric heats of adsorption, estimated by the Clausius-Clapeyron equation, are also higher for toluene compared to n-heptane. They were found to depend on framework microporosity of the relevant SBA-15 samples. The isosteric heats of adsorption for all sorbates decrease with increased loading and approach the heats of evaporation of the respective sorbate. The adsorption capacities of SBA-15 samples are significantly higher than those of silicalite, i.e., the MFI zeolite silica analogue. In contrast to that, the isosteric heats of adsorption in the mesopore channels of SBA-15 were found to be much smaller. This result also suggests that SBA-15 can potentially be a good candidate for separation of C(7) hydrocarbons.

Structure and diffusion characterization of SBA-15 materials.

In situ formation of the micro- and mesoporous structures of SBA-15 materials was investigated. It was found that the structure is significantly different from that for cylindrical or hexagonal pores, which suggests that the SBA-15 is more complex than an array of hexagonally ordered channels. Nitrogen adsorption isotherms at 77 K provided evidence that large (primary) mesopores are accompanied by a certain amount of significantly smaller pores with a broad distribution in the micropore/small-mesopore range within the mesoporous walls of main channels. It was found that the microporosity can be controlled by the time of heating as well as the synthesis temperature. The diffusion properties of n-heptane as a probe molecule in four selected SBA-15 samples with different micropore volumes were studied by the standard zero length column technique and related to their structural characteristics. The results have shown that the diffusion process involving n-heptane at a low concentration level takes place inside the walls of main mesoporous channels and depends on the relative content of micropores. In the samples that have a relatively high content of micropores, n-heptane diffusivities are relatively low, their activation energies are high, and the process is similar to diffusion in typical microporous adsorbents, like zeolites. As the micropore content is decreased, diffusion becomes more and more controlled by secondary mesopores of the intrawall pore structure, rendering diffusion faster and activation energies lower.