Synthesis of nanoscale zero-valent iron loaded chitosan for synergistically enhanced removal of U(VI) based on adsorption and reduction.

In this study, chitosan (CS) loading well-dispersed nanoscale zero-valent iron (NZVI/CS) was successfully prepared via the liquid-phase reduction method. Characterizations of the NZVI/CS with high-resolution transmission electron microscopy and X-ray diffraction suggested that the as-prepared NZVI/CS comprised numerous dispersed Fe0 nanoparticles. Synergistic adsorption and reduction occurred during the removal process based on X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. Influence of pH, contract time and temperature on U(VI) removal were investigated. The high removal capacity and rapid removal kinetics were predominately ascribed to the existence of well-distributed NZVI, which could rapidly reduce U(VI) into U(IV). The removal process could be better depicted by the Langmuir isotherm model and the pseudo-second-order kinetic model. The thermodynamic parameters showed that the removal process was exothermic. These findings indicate that the synthesized NZVI/CS composites have potential application for the removal of U(VI) from the sewage water.

Ultra-thin iron phosphate nanosheets for high efficient U(VI) adsorption.

In this study, the ultra-thin iron phosphate Fe7(PO4)6 nanosheets (FP1) with fine-controlled morphology, has been designed as a new two-dimensional (2D) material for uranium adsorption. Due to its unique high accessible 2D structure, atom-dispersed phosphate/iron anchor groups and high specific surface area (27.77 m2⋅g-1), FP1 shows an extreme-high U(VI) adsorption capacity (704.23 mg·g-1 at 298 K, pH = 5.0 ± 0.1), which is about 27 times of conventional 3D Fe7(PO4)6 (24.51 mg·g-1 -sample FP2) and higher than most 2D absorbent materials, showing a great value in the treatment of radioactive wastewater. According to the adsorption results, the sorption between U(VI) and FP1 is spontaneous and endothermic, and can be conformed to single molecular layer adsorption. Based on the analyses of FESEM, EDS, Mapping, FT-IR and XRD after adsorption, the possibile adsorption mechanism can be described as a Monolayer Surface Complexation and Stacking mode (MSCS-Mode). Additionally, the research not only provide a novel preparing method for 2D phosphate materials but also pave a new pathway to study other two-dimensional adsorption materials.

Exploration of the adsorption performance and mechanism of zeolitic imidazolate framework-8@graphene oxide for Pb(II) and 1-naphthylamine from aqueous solution.

A novel composite of zeolitic imidazolate framework grown on graphene oxide (ZIF-8@GO) was successfully prepared and used for the adsorption of Pb(II) and 1-naphthylamine from aqueous solutions. The effects of contact time, pH, ionic strength and temperature on the adsorption performance of ZIF-8@GO was investigated by batch experiments. Compared to the bare ZIF-8 and GO, the ZIF-8@GO exhibited a significant increase in the adsorption for Pb(II) and 1-naphthylamine. The maximum adsorption capacities of ZIF-8@GO towards Pb(II) and 1-naphthylamine reached 356.0 and 171.3 mg/g at 293 K, respectively. Besides, the basic physicochemical properties of ZIF-8@GO were characterized by Scanning electron microscope, X-ray diffraction, and Fourier transform infrared spectroscopy tests. The results revealed that ZIF-8@GO had large specific surface area, abundant functional groups and active sites on the surface, which could promote the adsorption of ZIF-8@GO for pollutants. In addition, based on zeta potential and X-ray photoelectron spectroscopy analysis, the primary adsorption mechanisms between ZIF-8@GO and Pb(II) were the surface complexation and electrostatic attraction, and the π-π interactions mainly contributed to the adsorption of 1-naphthylamine. In conclusion, as a new composite, ZIF-8@GO provides a reference idea for the removal of heavy metal ions and organic pollutants from water system.

Preparation of an Fe2Ni MOF on nickel foam as an efficient and stable electrocatalyst for the oxygen evolution reaction.

Metal-organic frameworks (MOFs) as versatile templates for preparing transition metal compounds has received wide attention. Benefiting from their diversified spatial structure and controllable chemical constituents, they have become a research hotspot in the field of electrocatalytic water splitting. Herein, Fe2Ni-MIL-88B MOF on nickel foam (Fe2Ni MOF/NF) has been prepared through a one-pot method growth process. Compared with Fe MOF/NF and Ni MOF/NF, the interaction between Fe3+ and Ni2+ in Fe2Ni MOF/NF accelerates the electron transfer through the oxygen of the ligand, leading to increased 3d orbital electron density of Ni, which enhances the activity of the oxygen evolution reaction (OER) in alkaline solution. Fe2Ni MOF/NF provides a current density of 10 mA cm-2 at a low overpotential of 222 mV, and its Tafel slope is also very small, reaching 42.39 mV dec-1. The success of the present Fe2Ni MOF/NF catalyst is attributed to the abundant active centers, the bimetallic clusters Fe2Ni-MIL-88B, the positive coupling effect between Ni and Fe metal ions in the MOF, and synergistic effect between the MOF and NF. Besides, Fe2Ni MOF/NF possesses excellent stability over 50 h of continuous operation, providing feasibility for commercial use.

Nanoscale zero-valent iron/magnetite carbon composites for highly efficient immobilization of U(VI).

Nanoscale zerovalent iron/magnetic carbon (NZVI/MC) composites were successfully synthesized by simply calcining yellow pine and iron precursors. NZVI/MC pyrolyzed at 800°C (NZVI/MC800) had a higher percentage of NZVI and displayed better resistance to aggregation and oxidation of NZVI than samples prepared at other temperatures. The NZVI/MC800 material was applied for the elimination of U(VI) from aqueous solutions. The results suggested that the NZVI/MC800 displayed excellent adsorption capacity (203.94 mg/g) toward U(VI). The significant adsorption capacity and fast adsorption kinetics were attributed to the presence of well-dispersed NZVI, which could quickly reduce U(VI) into U(IV), trapping the guest U(IV) in the porous biocarbon matrix. The removal of U(VI) on the NZVI/MC samples was strongly affected by solution pH. The NZVI/MC samples also displayed outstanding reusability for U(VI) removal after multiple cycles. These findings indicate that NZVI/MC has great potential for remediation of wastewater containing U(VI).

Adsorption of 17ß-estradiol from aqueous solutions by a novel hierarchically nitrogen-doped porous carbon.

A novel interconnected hierarchically nitrogen-doped porous carbon (IHNPC) derived from metal-organic framework-based composites was obtained via a facile method and applied as a superior material for the capture of 17ß-estradiol (E2) from aqueous solution. The adsorption kinetic and isotherm behaviors were well described by the pseudo-second-order and Langmuir models. Various thermodynamic parameters uncovered that E2 adsorption onto IHNPC was spontaneous and exothermic. Moreover, the adsorption rate of E2 by IHNPC didn't decrease with increasing water salinity in the presence of electrolyte ions and humic acids. Naturally occurring aquatic particles can enhance (i.e., Al2O3), decrease (i.e., kaolin and SiO2) or have no obvious effects (i.e., montmorillonite) on the adsorption rate of E2 by IHNPC. The high adsorption capacity and remarkable adsorption selectivity of IHNPC highlighted the application of IHNPC for the capture of E2 and provided understanding of the fate and transport of E2 in natural aquatic environments.

Complex dynamics of a neuron model with discontinuous magnetic induction and exposed to external radiation.

The last two decades have seen many literatures on the mathematical and computational analysis of neuronal activities resulting in many mathematical models to describe neuron. Many of those models have described the membrane potential of a neuron in terms of the leakage current and the synaptic inputs. Only recently researchers have proposed a new neuron model based on the electromagnetic induction theorem, which considers inner magnetic fluctuation and external electromagnetic radiation as a significant missing part that can participate in neural activity. While the flux coupling of the membrane is considered equivalent to a memductance function of a memristor, standard memductance model of α + 3 ß Ï• 2 has been used in the literatures, but in this paper we propose a new memductance function based on discontinuous flux coupling. Various dynamical properties of the neuron model with discontinuous flux coupling are studied and interestingly the proposed model shows hyperchaotic behavior which was not identified in the literatures. Furthermore, we consider a ring network of the proposed model and investigate whether the chimera state can emerge. The chimera state relates to the state with simultaneously coherence and incoherence in oscillatory networks and has received much attention in recent years.

Simultaneous adsorption and oxidative degradation of Bisphenol A by zero-valent iron/iron carbide nanoparticles encapsulated in N-doped carbon matrix.

The increased release and accumulation of Bisphenol A (BPA) in contaminated wastewater has resulted in the world wide concerns because of its potential negative effects on human health and aquatic ecosystems. Starting with metal-organic frameworks, we present a simple method to synthesize magnetic porous microcubes (N-doped Fe0/Fe3C@C) with graphitized shell and highly dispersed active kernel via the pyrolysis process under N2 atmosphere. Batch adsorption experimental results showed that N-doped Fe0/Fe3C@C had high adsorption capacity for BPA (∼138 mg g-1 at pH = 7 and 298 K). Degradation of BPA adsorbed on N-doped Fe0/Fe3C@C was further investigated as a function of BPA concentration, persulfate amount, temperature and solution pH. It was found that potassium peroxodisulfate could be activated by N-doped Fe0/Fe3C@C, and a large number of free radicals were generated which was crucial for the degradation of BPA. The concentration of BPA was barely changed in the individual persulfate system. BPA (10 mg L-1) was almost completely degraded within 60 min in the presence of N-doped Fe0/Fe3C@C (∼0.2 g L-1). When the BPA content increased to 25 mg L-1, the removal efficiency of BPA achieved to 98.4% after 150 min. From the XRD, Raman, and XPS analysis, the main adsorption mechanism of BPA was π-π interactions between the π orbital on the carbon basal planes and the electronic density in the BPA aromatic rings. While the superior degradation was attributed to the radical generation and evolution in phenol oxidation. This work not only proved the potential application of N-doped Fe0/Fe3C@C in the adsorption and degradation of BPA, but also opened the new possibilities to eliminate organic pollutants using this kind of magnetic materials in organic pollutants' cleanup.

Consumption-based greenhouse gas emissions accounting with capital stock change highlights dynamics of fast-developing countries.

Traditional consumption-based greenhouse gas emissions accounting attributed the gap between consumption-based and production-based emissions to international trade. Yet few attempts have analyzed the temporal deviation between current emissions and future consumption, which can be explained through changes in capital stock. Here we develop a dynamic model to incorporate capital stock change in consumption-based accounting. The new model is applied using global data for 1995-2009. Our results show that global emissions embodied in consumption determined by the new model are smaller than those obtained from the traditional model. The emissions embodied in global capital stock increased steadily during the period. However, capital plays very different roles in shaping consumption-based emissions for economies with different development characteristics. As a result, the dynamic model yields similar consumption-based emissions estimation for many developed countries comparing with the traditional model, but it highlights the dynamics of fast-developing countries.

Enhanced Electron Injection and Exciton Confinement for Pure Blue Quantum-Dot Light-Emitting Diodes by Introducing Partially Oxidized Aluminum Cathode.

Stable and efficient red (R), green (G), and blue (B) light sources based on solution-processed quantum dots (QDs) play important roles in next-generation displays and solid-state lighting technologies. The brightness and efficiency of blue QDs-based light-emitting diodes (LEDs) remain inferior to their red and green counterparts, due to the inherently unfavorable energy levels of different colors of light. To solve these problems, a device structure should be designed to balance the injection holes and electrons into the emissive QD layer. Herein, through a simple autoxidation strategy, pure blue QD-LEDs which are highly bright and efficient are demonstrated, with a structure of ITO/PEDOT:PSS/Poly-TPD/QDs/Al:Al2O3. The autoxidized Al:Al2O3 cathode can effectively balance the injected charges and enhance radiative recombination without introducing an additional electron transport layer (ETL). As a result, high color-saturated blue QD-LEDs are achieved with a maximum luminance over 13,000 cd m-2, and a maximum current efficiency of 1.15 cd A-1. The easily controlled autoxidation procedure paves the way for achieving high-performance blue QD-LEDs.

l-cysteine intercalated layered double hydroxide for highly efficient capture of U(VI) from aqueous solutions.

l-cysteine intercalated Mg/Al layered double hydroxide (Cys-LDH) composites were fabricated and applied for treating the U(VI) contaminated wastewater under various conditions. Interaction mechanisms and adsorption properties were investigated by using batch experiments with spectroscopy analysis. The adsorption isotherms and kinetics were fitted perfectly with the Langmuir isotherm and the pseudo-second-order model, respectively. The significant maximum adsorption capacity of Cys-LDH (211.58 mg/g) compared to LDH was attributed to the larger number of functional groups on Cys-LDH. The presence of humic acid (HA) decreased U(VI) elimination on Cys-LDH at high pH but increased U(VI) removal at low pH. Typically, the presence of various anions (such as NO3-, Cl-, ClO4- and SO42-) did not obviously affect U(VI) adsorption on Cys-LDH, while the coexisted CO32- significantly affected U(VI) elimination. The predominate adsorption were determined to be the formation of Cys-U(VI)-Cys complexes with cysteine in the Cys-LDH interlayers. The results demonstrated that the Cys-LDH are promising adsorbents for efficient elimination and extraction of radionuclides in actual environmental contamination management.

Adsorption and co-adsorption of graphene oxide and Ni(II) on iron oxides: A spectroscopic and microscopic investigation.

Graphene oxide (GO) may strongly interact with toxic metal ions and mineral particles upon release into the soil environment. We evaluated the mutual effects between GO and Ni (Ni(II)) with regard to their adsorption and co-adsorption on two minerals (goethite and hematite) in aqueous phase. Results indicated that GO and Ni could mutually facilitate the adsorption of each other on both goethite and hematite over a wide pH range. Addition of Ni promoted GO co-adsorption mainly due to the increased positive charge of minerals and cation-π interactions, while the presence of GO enhanced Ni co-adsorption predominantly due to neutralization of positive charge and strong interaction with oxygen-containing functional groups on adsorbed GO. Increasing adsorption of GO and Ni on minerals as they coexist may thus reduce their mobility in soil. Extended X-ray absorption fine structure (EXAFS) spectroscopy data revealed that GO altered the microstructure of Ni on minerals, i.e., Ni formed edge-sharing surface species (at RNi-Fe∼3.2 Å) without GO, while a GO-bridging ternary surface complexes (at RNi-C∼2.49 Å and RNi-Fe∼4.23 Å) was formed with GO. These findings improved the understanding of potential fate and toxicity of GO as well as the partitioning processes of Ni ions in aquatic and soil environments.

Molecular Engineering of Simple Benzene-Arylamine Hole-Transporting Materials for Perovskite Solar Cells.

Three benzene-arylamine hole-transporting materials (HTMs) with different numbers of terminal groups were prepared. It is noted that the molecule with three arms (H-Tri) shows a lower highest occupied molecular orbital level and a better film morphology on perovskite layer than the molecules with two or four arms (H-Di, H-Tetra). When these molecules were applied to the perovskite solar cells, the H-Tri-based one showed better performance compared with the H-Di- or H-Tetra-based ones. Photoluminescence and impedance spectroscopy demonstrate that H-Tri can improve the hole-electron separation efficiency and decrease the charge recombination, thus leading to a better performance. Moreover, the H-Tri-based device shows a comparable performance and a much less materials cost than the conventional spiro-OMeTAD. Therefore, we have presented a new low-cost and high-performance HTM through simple molecular engineering.

Electromagneto squeezing rotational flow of Carbon (C)-Water (H2O) kerosene oil nanofluid past a Riga plate: A numerical study.

This article predicts the electromagneto squeezing rotational flow of carbon-water nanofluid between two stretchable Riga plates. Riga plate is known as electromagnetic actuator which is the combination of permanent magnets and a span wise aligned array of alternating electrodes mounted on a plane surface. Mathematical model is developed for the flow problem with the phenomena of melting heat transfer, viscous dissipation and heat generation/absorption. Water and kerosene oil are utilized as the base fluids whereas single and multi-wall carbon nanotubes as the nanomaterials. Numerical solutions of the dimensionless problems are constructed by using built in shooting method. The correlation expressions for Nusselt number and skin friction coefficient are developed and examined through numerical data. Characteristics of numerous relevant parameters on the dimensionless temperature and velocity are sketched and discussed. Horizontal velocity is found to enhance for higher modified Hartman number.

Tailoring the nickel nanoparticles anchored on the surface of Fe3O4@SiO2 spheres for nanocatalysis.

Herein, we report an efficient and universal strategy for synthesizing a unique triple-shell structured Fe3O4@SiO2@C-Ni hybrid composite. Firstly, the Fe3O4 cores were synthesized by hydrothermal reaction, and sequentially coated with SiO2 and a thin layer of nickel-ion-doped resin-formaldehyde (RF-Ni2+) using an extended Stöber method. This was followed by carbonization to produce the Fe3O4@SiO2@C-Ni nanocomposites with metallic nickel nanoparticles embedded in an RF-derived thin graphic carbon layer. Interestingly, the thin SiO2 spacer layer between RF-Ni2+ and Fe3O4 plays a critical role on adjusting the size and density of the nickel nanoparticles on the surface of Fe3O4@SiO2 nanospheres. The detailed tailoring mechanism is explicitly discussed, and it is shown that the iron oxide core can react with the nickel nanoparticles without the SiO2 spacer layer, and the size and density of the nickel nanoparticles can be effectively controlled when the SiO2 layer exits. The multifunctional composites exhibit a significantly enhanced catalytic performance in the reduction of 4-nitrophenol (4-NP).

Sensitive determination of endogenous hydroxyl radical in live cell by a BODIPY based fluorescent probe.

The sensitive and selective fluorescence probe for hydroxyl radical analysis is of significance because hydroxyl radical plays key roles in many physiological and pathological processes. In this work, a novel organic fluorescence molecular probe OHP for hydroxyl radical is synthesized by a two-step route. The probe employs 4-bora-3a,4a-diaza-s-indacene (difluoroboron dipyrromethene, BODIPY) as the fluorophore and possesses relatively high fluorescence quantum yields (77.14%). Hydroxyl radical can rapidly react with the probe and quench the fluorescence in a good linear relationship (R2=0.9967). The limit of detection is determined to be as low as 11nM. In addition, it has been demonstrated that the probe has a good stability against pH and light illumination, low cytotoxicity and high biocompatibility. Cell culture experimental results show that the probe OHP is sensitive and selective for imaging and tracking endogenous hydroxyl radical in live cells.

Radiation effects on the mixed convection flow induced by an inclined stretching cylinder with non-uniform heat source/sink.

This study investigates the mixed convection flow of Jeffrey liquid by an impermeable inclined stretching cylinder. Thermal radiation and non-uniform heat source/sink are considered. The convective boundary conditions at surface are imposed. Nonlinear expressions of momentum, energy and concentration are transformed into dimensionless systems. Convergent homotopic solutions of the governing systems are worked out by employing homotopic procedure. Impact of physical variables on the velocity, temperature and concentration distributions are sketched and discussed. Numerical computations for skin friction coefficient, local Nusselt and Sherwood numbers are carried out. It is concluded that velocity field enhances for Deborah number while reverse situation is observed regarding ratio of relaxation to retardation times. Temperature and heat transfer rate are enhanced via larger thermal Biot number. Effect of Schmidt number on the concentration and local Sherwood number is quite reverse.

Synthesis of molybdenum disulfide/reduced graphene oxide composites for effective removal of Pb(II) from aqueous solutions.

In this work, a facile method was adopted to synthesize molybdenum disulfide/reduced graphene oxide (MoS2/rGO) composites through an l-cysteine-assisted hydrothermal technique. The as-prepared MoS2/rGO composites were firstly applied as adsorbents for efficient elimination of Pb(II) ions. Batch adsorption experiments showed that the adsorption of Pb(II) on MoS2/rGO followed pseudo-second-order kinetic model well. The adsorption of Pb(II) was intensely pH-dependent, ionic strength-dependent at pH < 9.0 and ionic strength-independent at pH > 9.0. The presence of humic acid (HA) enhanced Pb(II) adsorption obviously. The MoS2/rGO composites exhibited excellent adsorption capacity of 384.16mgg-1 at pH 5.0 and T=298.15K, which was superior to MoS2 (279.93mgg-1) and many other adsorbents. The thermodynamic parameters suggested that the adsorption process of Pb(II) on MoS2/rGO composites was spontaneous (ΔGθ<0) and endothermic (ΔHθ>0). The interaction of Pb(II) and MoS2/rGO was mainly dominated by electrostatic attraction and surface complexation between Pb(II) and oxygen-containing functional groups of MoS2/rGO. This work highlighted the application of MoS2/rGO as novel and promising materials in the efficient elimination of Pb(II) from contaminated water and industrial effluents in environmental pollution management.

New Insight into GO, Cadmium(II), Phosphate Interaction and Its Role in GO Colloidal Behavior.

This study establishes the relationship between the graphene oxide (GO) colloidal behavior and the co-adsorption of Cd(II) and phosphate (P(V)) on GO. Results reveal that the interactions among GO, Cd(II), and P(V) exhibit a significant dependence on solution chemistry and addition sequences and that these interactions subsequently affect the GO colloidal behavior. The GO aggregation is pH-dependent at pH < 4.0 and depends apparently on the binding ability of Cd(II) to GO at pH > 4.0. When the components were added simultaneously, the presence of P(V) enhances the GO binding capacity toward Cd(II), confirmed by theoretical calculation, resulting in the greater destabilizing influence of Cd(II) + P(V) on GO than Cd(II) at pH 3.0-9.5, while the formation of Cd3(PO4)2 precipitate leads to a lower destabilizing influence of Cd(II) + P(V) on GO than Cd(II) at pH > 9.5. Both pH and addition sequence affect the destabilizing ability of Cd(II) + P(V). These new insights are expected to provide valuable information not only for the application of GO as a potential adsorbent in multicomponent systems for heavy metal ion and oxyanion co-removal but also for the fate and risk assessment of GO after serving as heavy metal ion and oxyanion carrier.

Environmental Remediation and Application of Nanoscale Zero-Valent Iron and Its Composites for the Removal of Heavy Metal Ions: A Review.

The presence of heavy metals in the industrial effluents has recently been a challenging issue for human health. Efficient removal of heavy metal ions from environment is one of the most important issues from biological and environmental point of view, and many studies have been devoted to investigate the environmental behavior of nanoscale zerovalent iron (NZVI) for the removal of toxic heavy metal ions, present both in the surface and underground wastewater. The aim of this review is to show the excellent removal capacity and environmental remediation of NZVI-based materials for various heavy metal ions. A new look on NZVI-based materials (e.g., modified or matrix-supported NZVI materials) and possible interaction mechanism (e.g., adsorption, reduction and oxidation) and the latest environmental application. The effects of various environmental conditions (e.g., pH, temperature, coexisting oxy-anions and cations) and potential problems for the removal of heavy metal ions on NZVI-based materials with the DFT theoretical calculations and EXAFS technology are discussed. Research shows that NZVI-based materials have satisfactory removal capacities for heavy metal ions and play an important role in the environmental pollution cleanup. Possible improvement of NZVI-based materials and potential areas for future applications in environment remediation are also proposed.