Unexpected exfoliation and activity of nano poly(tetrafluoroethylene) particles from magnetic stir bars: Discovery and implication.

Magnetic stir bars are routinely used by most of researchers in the fields of chemistry, biology and environment etc. An incredible phenomenon, in which the magnetic stirring increased reaction rate by tens of times under ultrasound irradiation, impelled us to explore roles of magnetic stirring. Unexpectedly, the thimbleful nano PTFE particles, from shell of magnetic stir bar, were exfoliated during magnetic stirring and account for ultrahigh tribocatalytic and piezocatalytic activities under ultrasonic irradiation. Reactive oxygen species (ROS), such as hydroxyl radical (OH), superoxide radicals (O2-) and singlet oxygen (1O2) were generated in the present of PTFE under ultrasound irradiation, which is desired in the pollution control. The newly discovered PTFE activity, against the conventional wisdom that PTFE is inert, which also reminds the researchers that the trace amount of PTFE ground during magnetic stirring may inadvertently botch our experiments and introduce false positive results, especially involving routine magnetic stirring and ultrasound irradiation operation in laboratory. In addition, the safety and inertness of PTFE may require further review in PTFE-based commercial, industrial and biomedical settings.

Peroxydisulfate Activation and Singlet Oxygen Generation by Oxygen Vacancy for Degradation of Contaminants.

Oxygen vacancies (OVs) play a crucial role in the catalytic activity of metal-based catalysts; however, their activation mechanism toward peroxydisulfate (PDS) still lacks reasonable explanation. In this study, by taking bismuth bromide (BiOBr) as an example, we report an OV-mediated PDS activation process for degradation of bisphenol A (BPA) employing singlet oxygen (1O2) as the main reactive species under alkaline conditions. The experimental results show that the removal efficiency of BPA is proportional to the number of OVs and is highly related to the dosage of PDS and the catalyst. The surface OVs of BiOBr provide ideal sites for the inclusion of hydroxyl ions (HO-) to form BiIII-OH species, which are regarded as the major active sites for the adsorption and activation of PDS. Unexpectedly, the activation of PDS occurs through a nonradical mechanism mediated by 1O2, which is generated via multistep reactions, involving the formation of an intermediate superoxide radical (O2•-) and the redox cycle of Bi(III)/Bi(IV). This work is dedicated to the in-depth mechanism study into PDS activation over OV-rich BiOBr samples and provides a novel perspective for the activation of peroxides by defective materials in the absence of additional energy supply or aqueous transition metal ions.

Removal of model dyes on charged UF membranes: Experiment and simulation.

Charged ultrafiltration (UF) membranes can repel electrically charged molecules that are smaller than the size of the membrane pores and display high rejection of solutes, high flux, and low operation pressures compared to uncharged UF, nanofiltration (NF) and reverse osmosis (RO). Here, a charged UF membrane composite (PANI/PVDF) was prepared and regulated via electrochemically reversible control in portions of amine/imine functional groups of PANI. As a result, the permeability and rejection ratios of CR2- on charged PANI/PVDF, with PVDF as a control, increased from 19.6 to a maximum of 183.3 L m-2 h-1 bar-1 and from 3.4% to 74%, which expands the trade-off confine benefited from surface potential change from -12.21 mV to -25.26 mV, furtherly, the rejection ratio of CR2- on PANI/PVDF reached up to 93% via the electrochemical regulation. Finally, a fixed-charge model was built that well describes the steric and electric repulsion effects on membrane performance and the important roles of the electrochemically controllable surface charge. Moreover, the contour map of rejection ratios containing the ratio of molecular size vs the average pore size of the membrane (r/R = 0.2-1.0) and the zeta potential (-10 to -60 mV) were taken into account, which can be used to visually understand the rejection performance of membranes. This model is also appropriate for varying molecular sizes and for molecules with different charges. Our work opens a new horizon for the design of electrochemically controllable charged membranes to remove charged compounds.

ß-D-Galactose-Functionalized Pillar[5]arene With Interesting Planar-Chirality for Constructing Chiral Nanoparticles.

Planar-chiral pillar[5]arenes bearing ß-D-galactose substituents on both rims have been successfully synthesized and effectively separated by silica gel chromatography with a high yield. The obtained (S p )- and (R p )-ß-D-galactose functionalized pillar[5]arenes [(S p-D )-GP5 and (R p-D )-GP5] exhibit the S p and R p planar chirality. Furthermore, (S p-D )-GP5 and (R p-D )-GP5 can not racemize according to dynamic 1H NMR and CD spectra. Notably, GP5 is able to capture a guest molecule (DNS-CPT) to form a host-guest supramolecular amphiphile, which can further self-assemble into chiral nanoparticles with the S p and R p planar chirality of (S p-D )-GP5 and (R p-D )-GP5 still being retained, suggesting GP5 could be as reliable chiral sources to transfer the S p and R p planar chirality.

Adsorption and Reduction of Cr(VI) Together with Cr(III) Sequestration by Polyaniline Confined in Pores of Polystyrene Beads.

The simultaneous reduction and sequestration of Cr(VI) from wastewater is desirable as a cost-effective and environmentally friendly approach. In this study, we execute a one-step facile synthesis strategy on polyaniline (PANI) composites based on aniline adsorption and polymerization on pores of millimeter-scale polystyrene balls (PANI@PS). The well-defined PANI@PS increased the removal capacity of Cr(VI) by 5.4 times, going from 43.6 (bulky PANI) to 233.7 mg g-1 near neutral pH (6.0) instead of the pH 1-3 documented in other reports, which was higher than that of many reported adsorbents due to its porous structure, numerous interaction sites, and confinement effects in the polymer. Most importantly, PANI@PS could efficiently sequester positive Cr(III) after reducing Cr(VI) to Cr(III) due to its negative surface created by confinement effects confined to the nanopores of PS. Conversely, positively charged bulky PANI repelled electrostatically positive Cr(III); thus, additional precipitation or adsorption treatments were needed in practical applications. Moreover, a coating of PANI can protect PS, as a substrate and a composite, from irreversible damage due to the strong oxidation capacity of Cr(VI), which is another major concern in adsorbing strong oxidants using polymers. A novel strategy to regenerate the exhausted PANI@PS was efficiently executed based on the electrochemical redox reversibility of PANI. Finally, the comprehensive adsorption/reduction/sequestration of Cr on PANI@PS was elucidated in detail.

Hollow-spherical Co/N-C nanoparticle as an efficient electrocatalyst used in air cathode microbial fuel cell.

The hollow-spherical Co/N-C nanoparticle, which is synthesized via a simple hydrothermal reaction followed by heat treatment, is firstly used as electrocatalyst for oxygen reduction reaction (ORR) in air-cathode microbial fuel cell (MFC). The maximum power density of MFC with 10% Co/N-C air-cathode is as high as 2514±59mWm(-2), which is almost 174% higher than the control. The exchange current density (i0) of cathode equipped with 10% Co/N-C is 238% higher than that of untreated AC. While the total resistance of treated samples decreases from 13.017 to 10.255Ω. The intensity ratio of Raman D to G band (ID/IG) decreases from 0.93 (N-C) to 0.73 (Co/N-C), indicating the catalyst forms graphite structure. Both XRD and XPS testify that Co is bonded to N within graphitic sheets and serves as the active sites in ORR. The four-electron pathway of the Co/N-C also plays a crucial role in electrochemical catalytic activity. As a result, it can be expected that the as-synthesized Co/N-C, with extraordinary electro-catalytic performance towards ORR, will be a promising alternative to the state-of-the-art non-precious metal ORR electro-catalysts for electrochemical energy applications.

Iron-nitrogen-activated carbon as cathode catalyst to improve the power generation of single-chamber air-cathode microbial fuel cells.

In order to improve the performance of microbial fuel cell (MFC), iron-nitrogen-activated carbon (Fe-N-C) as an excellent oxygen reduction reaction (ORR) catalyst was prepared here using commercial activated carbon (AC) as matrix and employed in single chamber MFC. In MFC, the maximum power density increased to 2437±55 mW m(-2), which was 2 times of that with AC. The open circuit potential (OCP) of Fe-N-C cathode (0.47) was much higher than that of AC cathode (0.21 V). The R0 of Fe-N-C decreased by 47% from 14.36 Ω (AC) to 7.6 Ω (Fe-N-C). From X-ray photoelectron spectroscopy (XPS), pyridinic nitrogen, quaternary nitrogen and iron species were present, which played an important role in the ORR performance of Fe-N-C. These results demonstrated that the as-prepared Fe-N-C material provided a potential alternative to Pt in AC air cathode MFC for relatively desirable energy generation and wastewater treatment.

The performance and mechanism of modified activated carbon air cathode by non-stoichiometric nano Fe3O4 in the microbial fuel cell.

Cathodic catalyst is one of the key materials in microbial fuel cell (MFC). The addition of non-stoichiometric nano Fe3O4 in activated carbon (NSFe3O4/AC) air cathode was beneficial to boosting the charge transfer of the cathode accompanying with the enhancement of power performance in MFC. The air cathode modified by NSFe3O4 (5%, Wt%) increased the maximum power density by 83.3% from 780 mW/m(2) to 1430 mW/m(2) compared with bare air cathode. The modified cathodes showed enhanced electrochemical properties and appeared the maximum exchange current density of 18.71×10(-4) A/cm(2) for oxygen reduction reaction. The mechanism of oxygen reduction for the NSFe3O4/AC catalyst was a 4-electron pathway. The oxygen vacancy of the NSFe3O4 played a crucial role in electrochemical catalytic activity. The great catalytic performance made NSFe3O4 have a promising outlook applied in MFC.

Influence of different morphology of three-dimensional Cu(x)O with mixed facets modified air-cathodes on microbial fuel cell.

Three kinds of three-dimensional (3D) CuxO catalysts were prepared to modify activated carbon air-cathode using a facile electrochemical method with addition of surfactants. The maximum power density of MFC using SC-Cu air cathode (added sodium citrate into the electrolyte solution in electrodeposition process) was 1550±47 mW m(-2), almost 77% higher than AC cathode. Specifically, the charge transfer resistance significantly decreased by 89% from 9.3980 Ω to 1.0640 Ω compared to the control. Lumphy and mutually embedded filmy sheet structure were observed in SEM, which provided sufficient active sites for oxygen adsorption and diffusion. In XRD and TEM result, CuxO with mixed facets showed special structure which had a better performance. Crystallization condition of electrodeposited materials played a significant role in their nature electrochemical properties, morphology controlled by surfactant of CuxO exhibited high properties on the air-cathode MFC.

The addition of ortho-hexagon nano spinel Co3O4 to improve the performance of activated carbon air cathode microbial fuel cell.

Commercial Co3O4 and ortho-hexagon spinel nano-Co3O4 (OHSNC) were doped in the AC at a different percentage (5%, 10% and 15%) to enhance the performance of microbial fuel cell (MFC). The maximum power density of MFC with 10% OHSNC doped cathode was 1500±14 mW m(-2), which was 97.36% and 41.24% higher than that with the bare AC air cathode and commercial Co3O4 respectively. The electrocatalytic behavior for their better performance was discussed in detail with the help of various structural and electrochemical techniques. The OHSNC was characterized via X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM). The results showed that the improved performance owed to the enhancement of both kinetics activity and the number of electron transfer in the ORR, and the internal resistance was largely reduced. Therefore, OHSNC was proved to be an excellent cathodic catalyst in AC air cathode MFC.

N-type Cu2O doped activated carbon as catalyst for improving power generation of air cathode microbial fuel cells.

A novel n-type Cu2O doped activated carbon (AC) air cathode (Cu/AC) was developed as an alternative to Pt electrode for oxygen reduction in microbial fuel cells (MFCs). The maximum power density of MFCs using this novel air cathode was as high as 1390±76mWm(-2), almost 59% higher than the bare AC air cathode. Specifically, the resistance including total resistance and charge transfer resistance significantly decreased comparing to the control. Tafel curve also showed the faster electro-transfer kinetics of Cu/AC with exchange current density of 1.03×10(-3)Acm(-2), which was 69% higher than the control. Ribbon-like Cu2O was deposited on the surface of AC with the mesopore surface area increasing. Cubic Cu2O crystals exclusively expose (111) planes with the interplanar crystal spacing of 2.48Å, which was the dominate active sites for oxygen reduction reaction (ORR). N-type Cu2O with oxygen vacancies played crucial roles in electrochemical catalytic activity.

The performance of phosphorus (P)-doped activated carbon as a catalyst in air-cathode microbial fuel cells.

To observe the influence of P-doped activated carbon (AC) in air-cathode microbial fuel cells (MFCs), AC was treated with H3PO4 (1M) at 80°C and 400°C respectively, and then was used as catalyst layer in the air-cathode. The maximum power densities were: 1096±33mW/m(2) (SP2, AC treated at 400°C), 954±36mW/m(2) (SP1, AC treated at 80°C), which were 55%, 35% higher than the control (708±27mW/m(2), untreated AC), respectively. The results of electrochemical impedance spectroscopy (EIS) and the Brunauer-Emmett-Teller (BET) showed that the total resistance was decreased and the pore structure was changed. The analysis of X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) demonstrated that P-doped functional group was produced in SP2, which caused the 15% greater power density than SP1 by increasing O2 adsorption. What is more important, the chemically modified method is simple and economical.