Chemically modified organic/inorganic nanoporous composite particles for the adsorption of reactive black 5 from aqueous solution

In the present work, we report a chemically modified polyacrylamide/silica nanoporous composite adsorbent for the removal of reactive black 5 (RB5) azo dye from aqueous solutions. The composite adsorbent was synthesized in a packed bed and modified by ethylenediamine (EDA). The adsorbent was characterized by Fourier transformation infrared (FT-IR), thermogravimetric analysis (TGA), thermoporometry, Brunauer, Emmett and Teller (BET) method and scanning electron microscopy (SEM). Mechanical stability of the adsorbent was examined in a packed bed by following the back-pressure of the column. Pore diameter of the composite adsorbent in dry and wet states was estimated to be about 18.71 nm and 12.61 nm, respectively. Adsorption experiments were performed in batch mode and effect of various operational parameters on the adsorption capability of the adsorbent was studied systematically. The maximum adsorption capacity of the modified composites was found to be 454.5 mg RB5/g of adsorbent. The equilibrium data were analyzed by Langmuir, Freundlich, Sips, BET and Redlich–Peterson isotherm models and found to fit well to the BET isotherm. The data kinetically followed the pseudo-second-order model. High adsorption capacity, fast removal mechanism, and good mechanical stability are three advantages of the presented composite for the removal of RB5.     

Preparation of Bi2Ti2O7/TiO2 nanocomposites and their photocatalytic performance under visible light irradiation

To improve visible-light-driven photocatalytic activity of TiO₂, the octahedral Bi₂Ti₂O₇ nanoparticles have been successfully supported on TiO₂ nanotubes (Bi₂Ti₂O₇/TiO₂) for the first time by a simple hydrothermal method. The structure and electro-optical property of the Bi₂Ti₂O₇/TiO₂ were characterized in detail. The obtained Bi₂Ti₂O₇/TiO₂ exhibited a markedly enhanced photocatalytic activity and good stability for degradation of organic pollutants under visible light. The study presents a new way to synthesize Bi₂Ti₂O₇/TiO₂ using TiO₂ nanotubes as both supporter and reactant.     

Enhanced properties for visible-light-driven photocatalysis of Ag nanoparticle modified Bi2MoO6 nanoplates

The visible light driven Bi₂MoO₆ photocatalyst doped with different contents of Ag nanoparticles was successfully synthesized by a combination of hydrothermal and sonochemical methods. The as-synthesized samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning and transmission electron microscopy (SEM and TEM) and UV–visible spectroscopy to investigate crystalline structure, morphology, composition and photocatalytic properties. XRD patterns and TEM images of the samples revealed pure phase orthorhombic Bi₂MoO₆ nanoplates without any detection of Ag dopant due to its low concentration and very tiny particle size. TEM images showed that Ag nanoparticles with the size of 10–15 nm were dispersed randomly on the surface of Bi₂MoO₆. The XPS analysis of Ag/Bi₂MoO₆ nanocomposites revealed the presence of additional metallic Ag. Photocatalytic activities of the Ag/Bi₂MoO₆ nanocomposites were evaluated by determining the degradation of rhodamine B (RhB) under visible light radiation. In this research, the 10 wt% Ag/Bi₂MoO₆ nanocomposites showed the best photocatalytic activity. The results suggest that the dispersion of Ag nanoparticles on the surface of Bi₂MoO₆ significantly enhances its photocatalytic activity.     

Theoretical investigation of solvent effects on the selective hydrogenation of furfural over Pt(111)

It was well known that solvent effect plays a very important role in the catalytic reaction. There are many theoretical studies on the solvent effect in homogeneous catalysis while there are few theoretical studies on the solvent effect in the heterogeneous catalytic reaction and there has been no work to investigate the solvent effect on furfural transformation in heterogeneous catalysis. In the present work, both the density functional calculations and the microkinetic analysis were performed to study the selective hydrogenation of furfural over Pt(111) in the presence of methanol as well as toluene and compared with that in the gas condition. The present results indicated that the methanol can enhance the adsorption strength of furfural and other oxygen-containing reaction species due to its relatively strong polarity properties and this can be a main reason for solvent-induced high activity and selectivity. Another reason is that reaction paths study showed that the presence of methanol solvent makes the dehydrogenation of furfural less thermochemical due to the fact that furfural is more stabilized than that of dehydrogenation species, and methanol also has an inhibition effect on the dehydrogenation of furfural in the kinetic aspect, and further energetic span theory proves highest activity and selectivity for hydrogenation in methanol solvent of vapor, methanol and toluene. Moreover, microkinetic model simulation demonstrated that the activity and selectivity of hydrogenation in methanol is both higher than that in vapor and toluene. The much higher activity in methanol is due to the stabilized adsorbed reactants in the surface, which leads to a higher surface coverage of furfural. It might be proposed based on the present work that a solvent with relatively strong polarity may be favorable for the high selective hydrogenation of furfural.     

Large piezoelectricity and potentially activated polarization reorientation around relaxor MPB in complex perovskite

Improving piezoelectric performance is always favorable to further enhance the sensitivity and accuracy of piezoelectric devices. Here, a complex piezoelectric system of Pb(Ni_1/3Nb_2/3)O₃-Pb(Yb_1/2Nb_1/2)O₃-Pb(Hf_0.1Ti_0.9)O₃ is designed and investigated in detail. Optimized piezoelectric response of ～ 880 pC/N is achieved at the composition of 0.51PNN-0.09PYN-0.40PHT. The characterization of TEM and In-situ high-energy synchrotron diffraction indicate that nanodomain growth and microdomain switching occurs in succession at around coercive electric field. Most interestingly, the coexisted tetragonal and rhombohedral-like phase transforms into multiple monoclinic-like phases with polarization vectors aligned as close to the electric field direction as possible under the strong electric field. The enhanced polarization instability in this complex morphotropic phase boundary sample should be ascribed to the strong local heterogeneity. The novel polarization rotation behavior found in this work would be important guidance for designing high-performance piezoceramics.     

Probing the degenerate pattern growth of {100}<011> orientation in a directionally solidified Al-4.5 wt% Cu alloy

Degenerate pattern is a seemingly disordered morphology but it exhibits the inherently ordered crystal connected with tip-splitting and limited stability which makes it difficult to observe in the metallic system. Here we employ (100)[011] orientated planar-front seeds using directional solidification and reveal the fundamental origins of the degenerate pattern growth in an Al-4.5 wt% Cu alloy. We find that the spacing of the tip-splitting (λ) in the degenerate of the alloys followed a power law, λ∝V^−0.5, and the frequency (f) of the splitting was related to the growth velocity (V) by ƒ∝V^1.5. The dimensionless growth direction (θ/θ₀) increased monotonously and approached 0.6 with faster velocity, attributed to its anisotropy in the interface kinetics. Once growth velocity exceeded a threshold, two types of pattern transitions from degenerate to regular dendrites were proposed. One of them exhibited a random and chaotic mode and the other underwent a rotation in growth direction.     

Hydrogen from wet air and sunlight in a tandem photoelectrochemical cell

A solid-state photoelectrochemical (SSPEC) cell is an attractive approach for solar water splitting, especially when it comes to monolithic device design. In a SSPEC cell the electrodes distance is minimized, while the use of polymer-based membranes alleviates the need for liquid electrolytes, and at the same time they can separate the anode from the cathode. In this work, we have made and tested, firstly, a SSPEC cell with a Pt/C electrocatalyst as the cathode electrode, under purely gaseous conditions. The anode was supplied with air of 80% relative humidity (RH) and the cathode with argon. Secondly, we replaced the Pt/C cathode with a photocathode consisting of 2D photocatalytic g-C₃N₄, which was placed in tandem with the photoanode (tandem-SSPEC). The tandem configuration showed a three-fold enhancement in the obtained photovoltage and a steady-state photocurrent density. The mechanism of operation is discussed in view of recent advances in surface proton conduction in absorbed water layers. The presented SSPEC cell is based on earth-abundant materials and provides a way towards systems of artificial photosynthesis, especially for areas where water sources are scarce and electrical grid infrastructure is limited or nonexistent. The only requirements to make hydrogen are humidity and sunlight.     

Performance improvement of conventional and inverted polymer solar cells with hydrophobic fluoropolymer as nonvolatile processing additive

The morphology of the photoactive layer critically affects the performance of the bulk heterojunction polymer solar cells (PSCs). To control the morphology, we introduced a hydrophobic fluoropolymer polyvinylidene fluoride (PVDF) as nonvolatile additive into the P3HT:PCBM active layer. The effect of PVDF on the surface and the bulk morphology were investigated by atomic force microscope and transmission electron microscopy, respectively. Through the repulsive interactions between the hydrophilic PCBM and the hydrophobic PVDF, much more uniform phase separation with good P3HT crystallinity is formed within the active layer, resulting enhanced light harvesting and improved photovoltaic performance in conventional devices. The PCE of the conventional device can improve from 2.40% to 3.07% with PVDF additive. The PVDF distribution within the active layer was investigated by secondary ion mass spectroscopy, confirming a bottom distribution of PVDF. Therefore, inverted device structure was designed, and the PCE can improve from 2.81% to 3.45% with PVDF additive. Our findings suggest that PVDF is a promising nonvolatile processing additive for high performance polymer solar cells.     

Analysis of nitrogen oxide emissions from modern vehicles using hydrogen or other natural and synthetic fuels in combustion chamber

The paper presents a calculated analysis of the equilibrium emission of nitrogen oxides on the exhaust of carburetor and diesel internal combustion engines. The temperature of fuel oxidation is assumed to be 1,400 °C while the pressure for carburetor and diesel engines is assumed to be 60 atm and 80 atm respectively. The studies have been carried out for natural and synthetic fuels such as hydrogen, ethanol, methanol, petroleum, diesel fuel and methane at the excess air coefficient corresponding to the fuel oxidation temperature of 1,400 °C. In the paper, the method for calculating the equilibrium composition based on the equilibrium constant and mass conservation equations has been applied. It is shown that with an increase in pressure from 1 atm to 60 atm for carburetor engines and up to 80 atm for diesel engines, the reaction of nitrogen dioxide formation may shift towards an increase in NO₂. The formation of NO may be not affected by the increase in pressure by virtue of the fact that the reaction proceeds without changes in the amount. It has been determined that NO is the major atmospheric pollutant. However, it would be advisable to use more extensively the fuels characterized by the lowest output of nitrogen dioxide (methane and methanol), since nitrogen dioxide (NO₂) related to the 2nd hazard class is appeared to be the most dangerous to humans. It has been revealed that the reduction in oxidation temperature using hydrogen as a fuel for electrochemical current generators may allow reducing nitrogen oxide emissions by more than an order of magnitude as compared to the best results for ICE.