Preparation of a Ti0.7W0.3O2/TiO2 nanocomposite interfacial photocatalyst and its photocatalytic degradation of phenol pollutants in wastewater.

A Ti0.7W0.3O2/TiO2 nanocomposite interfacial photocatalyst was designed and prepared for the photocatalytic degradation of phenol pollutants in wastewater. The detailed properties of the Ti0.7W0.3O2/TiO2 nanocomposite interface (NCI) were analyzed by XRD, SEM, EDX, DRS, UPS and XPS technologies, showing that anatase TiO2 nanospheres (NSs) were uniformly dispersed on the surface of rutile Ti0.7W0.3O2 nanoparticles (NPs) and formed the nanocomposite interface. The DRS and UPS results of 5 wt% Ti0.7W0.3O2/TiO2 NCI indicated a greatly broadened light response range with a wavelength shorter than 527 nm and a shorter band gap energy of 2.37 eV. The conduction band of TiO2 NSs, Ti0.7W0.3O2 NPs and 5 wt% Ti0.7W0.3O2/TiO2 NCI were measured based on the results of the valence band and band gap energy obtained via XPS and DRS, and then the energy level diagram of Ti0.7W0.3O2/TiO2 NCI was proposed. The photocatalytic degradation of phenol at Ti0.7W0.3O2/TiO2 NCI with different loading ratios of Ti0.7W0.3O2 NPs was investigated under optimum conditions (i.e., pH of 4.5, catalyst dosage of 0.45 g L-1 and phenol initial concentration of 95 ppm) under the illumination of ultraviolet visible light. Also, 5 wt% Ti0.7W0.3O2/TiO2 NCI exhibited the highest photocatalytic activity, with the initial rate constant (k) calculated as 0.09111 min-1. After recycling six times, Ti0.7W0.3O2/TiO2 NCI showed good stability and recyclability. The involvement of superoxide radicals in the initial reaction at Ti0.7W0.3O2/TiO2 NCI was evidenced by the use of a terephthalic acid (TA) fluorescent probe. Besides, UV-Vis spectroscopy, UHPLC-MS and GC-MS technologies were used to analyze the main intermediates in the photocatalytic degradation of phenol. The probable photocatalytic degradation mechanism of phenol at Ti0.7W0.3O2/TiO2 NCI was also proposed.

Macroporous monoliths with pH-induced switchable wettability for recyclable oil separation and recovery.

HYPOTHESIS: The effective separation and recovery of oils from water is important for the protections of ecosystems and the environment. Polymeric porous monoliths have been demonstrated as attractive absorbents for oil/water separation. However, the recyclability was mainly realized by squeezing, combustion, or centrifugation, which may restrict in elastic materials, destroy the adsorbates or need special apparatus. Thus it is desirable to developing monoliths with controllable oil absorption and desorption. EXPERIMENTS: A series of "smart" monoliths with pH-induced switchable wettability were fabricated by high internal phase emulsion (HIPE) polymerization and epoxide ring-opening for the incorporation of amine groups. The resultant monoliths and their wettabilities were examined using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), nitrogen adsorption/desorption and contact angle analysis, respectively. The oil separation efficiency and recyclability were evaluated. FINDINGS: The monoliths with macroporous structure can undergo switchable wettability under reversible pH stimulation. As an absorbent, the monoliths not only separated and recovered organic solvents and oils (including crude oil) from aqueous mixtures through a reversible and recyclable absorption and desorption process upon alternating the pH between 7.0 and 1.0, but also continuously expulsed oils from water surfaces in a continuous manner with the aid of external driving pressures. Moreover, the monoliths also allowed the effective separation of surfactant-free and surfactant-stabilized oil-in-water emulsions with high separation efficiency.

Giant Microgels with CO2-Induced On-Off, Selective, and Recyclable Adsorption for Anionic Dyes.

Adsorbents that are capable of controllable pollutants adsorption and release without secondary pollution are attractive in water treatment. Here, we propose eco-friendly CO2 as a trigger to switch the charge states and collapse-expansion transition of giant microgels consisting of hydrophilic acrylamide and hydrophobic 2-(diethylamino)ethyl methacrylate and demonstrated the on-off, selective, and recyclable adsorption of anionic dyes on microgels under CO2 stimulation. Apart from easy-handling separation from the water by a simple filtration process, the maximum adsorption capacity is as high as 821 mg g-1, and the adsorption isotherms and kinetics obeyed Langmuir isotherm and the pseudo-second-order kinetics models, respectively. The anionic dye can also be separated from the mixture solution using CO2-treated microgels. Moreover, a wastewater treatment prototype with microgel-packed column was fabricated. Under continuous flow condition, the dye was removed and recovered by alternative bubbling CO2 and flushing with aqueous alkali (pH 12). Thus, this type of microgels with CO2-induced protonation-deprotonation transition can serve as a cost-effective, environmentally friendly, and efficient adsorbent for water purification applications.

pH-Switchable and self-healable hydrogels based on ketone type acylhydrazone dynamic covalent bonds.

Stimuli-responsive hydrogels using dynamic covalent bonds (DCBs) as cross-links may exhibit simultaneously the stimuli-responsibility of the physical gels and stability of the chemical gels. We prepared well-defined, ketone-based polymers based on commercially available diacetone acrylamide (DAAM) by a reversible addition-fragmentation chain transfer (RAFT) polymerization technique. The polymers could react with hexanedihydrazide yielding hydrogels. The mechanics, flexible properties and gelator concentration of the hydrogels can be tuned by varying the ratio of DAAM. Gelation time and hydrogel stability were gravely affected by the pH of the surrounding medium. The hydrogels possess self-healing ability without any external stimuli and undergo switchable sol-gel transition by the alternation of pH. In addition, the hydrogels showed pH-responsive controlled release behavior for rhodamine B. These kinds of ketone-type acylhydrazone DCB hydrogels, avoiding the aldehyde component, may ameliorate their biocompatibility and find potential applications in biomedicines, tissue engineering, etc.

Preparation of cobalt-tetraphenylporphyrin/reduced graphene oxide nanocomposite and its application on hydrogen peroxide biosensor.

A novel cobalt-tetraphenylporphyrin/reduced graphene oxide (CoTPP/RGO) nanocomposite was prepared by a π-π stacking interaction and characterized by ultraviolet-visible absorption spectroscopy (UV-vis), Fourier transform infrared spectroscopy (FTIR) and electrochemical impedance spectroscopy (EIS). The CoTPP/RGO nanocomposite exhibited high electrocatalytic activity both for oxidation and reduction of H2O2. The current response was linear to H2O2 concentration with the concentration range from 1.0×10(-7) to 2.4×10(-3)molL(-1) (R=0.998) at the reductive potential of -0.20V and from 1.0×10(-7) to 4.6×10(-4)molL(-1) (R=0.996) at the oxidative potential of +0.50V. The H2O2 biosensor showed good anti-interfering ability towards oxidative interferences at the oxidative potential of +0.50V and good anti-interfering ability towards reductive interferences at the reductive potential of -0.20V.

Bilayer lipid membrane biosensor with enhanced stability for amperometric determination of hydrogen peroxide.

In this paper, a polydopamine (PDA) film is electropolymerized on the surface of bilayer lipid membrane (BLM) which is immobilized with horseradish peroxidase (HRP). The coverage of the PDA film on HRP/BLM electrode is monitored by electrochemical impedance spectroscopy (EIS). The electrocatalytic reduction of H(2)O(2) at the PDA/HRP/BLM electrode is studied by means of cyclic voltammetry (CV). The biosensor has a fast response to H(2)O(2) of less than 5s and an excellent linear relationship is obtained in the concentration range from 2.5×10(-7) to 3.1×10(-3) molL(-1), with a detection limit of 1.0×10(-7) molL(-1) (S/N=3). The response current of BLM/HRP/PDA biosensor retains 84% of its original response after being stored in 0.1 molL(-1) pH 7.0 PBS at 4°C for 3 weeks. The selectivity, repeatability, and storage stability of PDA/HRP/BLM biosensor are greatly enhanced by the coverage of polydopamine film on BLM.

Electrochemical biosensor with pH regulation of CNTs/HRP multilayer for phenols.

An amperometric horseradish peroxidase (HRP) biosensor based on multilayer films containing carbon nanotubes (CNTs) and HRP was developed. With the pH regulation of the dispersion solution of CNTs, the sensitivity of the HRP multilayer film biosensor is tunable by the control of the dissociation of CNTs. The successful formation of multilayers was confirmed by UV-visible spectroscopy. The features of multilayers were characterized by SEM and electrochemical impedance spectrum (EIS). The performance of the HRP biosensor is reported for the amperometric detection of phenols. The biosensor presented a linear response for catechol from 9.1 × 10(-8) - 6.45 × 10(-5) mol/L, with a sensitivity of 0.00554 A · L/mol and a detection limit of 8.5 × 10(-8) mol/L. The study can provide a feasible simple approach for developing a new sensitivity tunable method for CNTs-based biosensors.

Improvement of amperometric glucose biosensor by the immobilization of FcCD inclusive complex and carbon nanotube.

A novel glucose biosensor was constructed by using ferrocene-carbonyl-beta-cyclodextrin (FcCD) inclusive complex as electron-transfer mediator and carbon nanotubes (CNTs) as electron-transfer promoter. FcCD inclusive complex and glucose oxidase (GOx) were covalently bonded to CNTs by poly-l-lysine (PLL) to fabricate a glucose biosensor. The electrocatalytic oxidation of glucose at the biosensor occurred at low potential below 200 mV, avoiding the interference of the main interfering substances in real samples containing a 5-times higher concentration of l-cysteine, ascorbic acid, and uric acid. The biosensor showed fast response for glucose. A broad linear range of glucose concentration from 1.0 x 10(-5) to 2.90 x 10(-3) M was obtained and the detection limit was 2.2 x 10(-6) M.

Self-assembly of ordered 3D Pd nanospheres at a liquid/liquid interface.

A novel route for the self-assembly of nanoparticles to nanospheres at a liquid/liquid interface has been developed to prepare palladium nanospheres. It has proved that the interface offers an excellent site and plays a key role in the self-assembly of nanoparticles to nanospheres. The palladium nanospheres are characterized by electron microscopy, energy-dispersive X-ray analysis, UV-visible spectroscopy, X-ray diffraction spectroscopy, and X-ray photoelectron spectroscopy. The mechanism of the self-assembly process is also proposed.

Approximate derivative calculated by using continuous wavelet transform.

A novel method of calculating approximate derivative of signals in analytical chemistry by using the continuous wavelet transform (CWT) is proposed. As compared with numerical differentiation, FT method and DWT method, fast calculation, and simple mathematical operation are remarkable advantages of CWT method. The signal-to-noise ratio (SNR) of approximate derivative of signals calculated by CWT method is easily enhanced only through appropriately adjusting the dilation, even in the case of very low SNR. Therefore, CWT method is a powerful tool for performing the approximate derivative calculation of signals in analytical chemistry. Additionally, the approximate second derivative evaluated via CWT method can be used to determine the peak potentials of the overlapping square wave voltammogram (SWV) of Cd(II) and In(III), and the results are very satisfactory.