Yolk–shell structured iron carbide/N-doped carbon composite as highly efficient and stable oxygen reduction reaction electrocatalyst

We report a simple route to synthesize iron carbide/carbon yolk–shell composite via a facile two-step process including polymerization of pyrrole using Fe₃O₄ as a sacrificial template to form a Fe₃O₄/polypyrrole composite, followed by annealing at high temperature in N₂ atmosphere. The yolk–shell composite, with iron carbide (Fe_2.5C) embedded in nitrogen-doped carbon layers, shows impressively high catalytic activity and stability for oxygen reduction reaction in alkaline solution. Both the pyridinic-N and graphic-N in the shell of Fe₃O₄–PPy-700, together with the Fe_2.5C confined in carbon layers are believed to be the active sites for the ORR.     

Preparation of magnetically separable Cu6/7Co1/7Fe2O4–graphene catalyst and its application in selective reduction of nitroarenes

A magnetically separable and highly active Co–Cu mixed spinel catalyst, Cu_6/7Co_1/7Fe₂O₄–graphene (Cu_6/7Co_1/7Fe₂O₄–G), was fabricated by a hydrothermal method. The results demonstrated that the Cu_6/7Co_1/7Fe₂O₄–G possessed excellent catalytic activity for the reduction of a broad range of nitroarenes in the presence of NaBH₄. The composite catalyst was efficient, stable, low-cost and could be easily recovered due to its magnetic separability.     

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.     

Copper–4,4′-dipyridyl coordination compound as solid reagent for spectrophotometric determination of reducing sugar employing a multicommutation approach

In this work a multicommuted flow system employing copper–4,4′- dipyridyl coordination compound as the solid-phase reagent for the spectrophotometric determination of reducing sugar was developed. The coordination compound was synthesized through a reaction of the 4,4′-dipyridyl and copper (II) nitrate, under hydrothermal conditions. The complex was characterized by infrared spectroscopy (FTIR), power X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectrometer (EDS) and thermogravimetric analysis (TGA). Based on the characterization, a multicommuted spectrophotometric procedure for the determination of reducing sugar using copper (II) complex as solid reagent is proposed. The proposed method was based on the redox reaction between a monosaccharide, such as fructose and glucose (reducing sugar) and Cu(II). This reaction, mediated in an alkaline medium, produces a yellow compound that can be determined by absorption electronic spectroscopy (λ_ABS = 420 nm). Under optimum experimental conditions, a linear response ranging from 1.0 to 20.0 g L⁻¹ (R = 0.9978 and n = 5), a detection (3σ criterion) and quantification (10σ criterion) limit estimated at 0.23 and 0.75 g L⁻¹, respectively, a standard deviation relative of 4.7% (n = 7), for a reference solution of 10.0 g L⁻¹ reducing sugar, and a sampling rate of 75 determinations per hour were achieved. The proposed system was applied to the determination of reducing sugars in coconut water and juices. The analysis of ten samples and the application of the t-test to the results found, and those obtained using reference procedures (AOAC), provided no significant differences at a 95% confidence level. This system enabled the analysis of reducing sugar with ease and simplicity, providing a significant economy of the solid reagent (600 μg per determination) and reducing effluent generation.     

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.     

Wet chemical synthesis of Gd+3 doped vanadium Oxide/MXene based mesoporous hierarchical architectures as advanced supercapacitor material

In this paper, Gd³⁺ doped V₂O₅/Ti₃C₂T_x MXene (GVO/MX) hierarchical architectures have been synthesized by wet chemical approach. As prepared GVO/MX composite, along undoped VO and unsupported GVO were well characterized by XRD, FESEM, EDX, FT-IR and BET techniques. Electrochemical performance of VO, GVO and GVO/MX was evaluated by CV, GCD and EIS measurements. Among the three electrodes, GVO/MX composite exhibited highest electrochemical activity with the optimum specific capacitance of 1024 Fg^-1 at 10 mVs^?1. The specific capacitance of GVO/MX was ～1.7 and ～3 times higher than unsupported GVO (585 Fg^-1) and VO (326 Fg^-1), respectively. The cyclic life of GVO/MX with capacitance retention 96.12% was observed at 60 mVs^?1. EIS measurements showed reduction in electrochemical impedance for GVO/MX as compared to GVO and VO. The corresponding impedance values of Rct and Resr for GVO/MX were calculated as 18 Ω and 1.8 Ω, respectively. The superior capacitive ability of GVO/MX can be ascribed to its unique morphology, short diffusion path and high surface area of fabricated composite. Considering it, the present work provides a feasible strategy to fabricate highly effective electrode materials for next generation energy storage devices.     

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.     

The effect of charge on the dihydrogen storage capacity of Sc2–C6H6

The effect of charge on the dihydrogen storage capacity of Sc₂–C₆H₆ has been investigated at B3LYP-D3/6-311G(d,p) level. The neutral system Sc₂–C₆H₆ can store 8H₂ with gravimetric density of 8.76 wt %, and one H₂ dissociates and bonds atomically on the scandium atom. The adsorption of 8H₂ on Sc₂–C₆H₆ is energetically favorable below 155 K. The atom-centered density matrix propagation (ADMP) molecular dynamics simulations show that Sc₂–C₆H₆ can adsorb 3H₂ within 1000 fs at 300K. Compared with Sc₂–C₆H₆, the charged systems can adsorb more hydrogen molecules with higher gravimetric density, and all the H₂ are adsorbed in the molecular form. The gravimetric densities of Sc₂–C₆H₆⁺ and Sc₂–C₆H₆²⁺ are 9.75 and 10.71 wt%. Moreover, the maximum adsorption of charged systems are favorable in wider temperature range. Most importantly, the ADMP-MD simulations indicate that Sc₂–C₆H₆²⁺ can adsorb 6 hydrogen molecules within 1000 fs at 300K. It can be found that the gravimetric density (6.72 wt%) of Sc₂–C₆H₆²⁺ still exceeds the target of US Department of Energy (DOE) under ambient conditions.     

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.