Co2FeO4@rGO composite: Towards trifunctional water splitting in alkaline media

Development of efficient, low cost and multifunctional electrocatalysts for water splitting to harvest hydrogen fuels is a challenging task, but the combination of carbon materials with transition metal-based compounds is providing a unique and attractive strategy. Herein, composite systems based on cobalt ferrite oxide-reduced graphene oxide (Co₂FeO₄) @(rGO) using simultaneous hydrothermal and chemical reduction methods have been prepared. The proposed study eliminates one step associated with the conversion of GO into rGO as it uses direct GO during the synthesis of cobalt ferrite oxide, consequently rGO based hybrid system is achieved in-situ significantly, the optimized Co₂FeO₄@rGO composite has revealed an outstanding multifunctional applications related to both oxygen evolution reaction (OER) and hydrogen counterpart (HER). Various metal oxidation states and oxygen vacancies at the surface of Co₂FeO₄@rGO composites guided the multifunctional surface properties. The optimized Co₂FeO₄@rGO composite presents excellent multifunctional properties with onset potential of 0.60 V for ORR, an overpotential of 240 mV at a 20 mAcm^?2 for OER and 320 mV at a 10 mAcm^?2 for HER respectively. Results revealed that these multifunctional properties of the optimized Co₂FeO₄@ rGO composite are associated with high electrical conductivity, high density of active sites, crystal defects, oxygen vacancies, and favorable electronic structure arisinng from the substitution of Fe for Co atoms in binary spinel oxide phase. These surface features synergistically uplifted the electrocatalytic properties of Co₂FeO₄@rGO composites. The multifunctional properties of the Co₂FeO₄@ rGO composite could be of high interest for its use in a wide range of applications in sustainable and renewable energy fields.     

Nonlinearity in regulating the metal to insulator transition of ReNiO3 towards low temperature range

Among the existing material family of the correlated oxides, the rare earth nickelates (ReNiO₃) exhibit broadly adjustable metal to insulator transition (MIT) properties that enables correlated electronic applications, such as thermistors, thermochromics, and logical devices. Nevertheless, how to accurately control the critical temperature (T_MIT) of ReNiO₃ via the co-occupation of the rare-earth elements is yet worthy to be further explored. Herein, we demonstrate the non-linearity in adjusting the T_MIT of ReNiO₃ towards lower temperatures via introducing Pr co-occupation within ReNiO₃ (e.g., Pr_xNd_1-xNiO₃ and Pr_xSm_1-xNiO₃) as synthesized by KCl molten-salt assisted high oxygen pressure reaction approach. Although the T_MIT is effectively reduced via Pr substitution, it does not strictly follow a linear relationship, in particular, when there is large difference in the ionic radius of the co-occupation rare-earth elements. Furthermore, the most significant deviation in T_MIT from the expected linear relationship appears at an equal co-occupation ratio of the two different rare-earth elements, while the abruption in the variation of resistivity across T_MIT is also reduced. The present work highlights the importance to use adjacent rare-earth elements with co-occupation ratio away from 1:1 for achieving more linear adjustment in designing the metal to insulator transition properties for ReNiO₃.     

Tuning of shear thickening behavior and elastic strength of polyvinylidene fluoride via doping of ZnO-graphene

ZnO rice like nonarchitects are grafted on the graphene carbon core via a rapid microwave synthesis route. The prepared grafted systems are characterized via XRD, SEM, RAMAN, and XPS to examined the structural and morphological parameters. Zinc oxide grafted graphene sheets (ZnO-G) are further doped in β-phase of polyvinylidene fluoride (PVDF) to prepare the polymer nanocomposites (PNCs) via mixed solvent approach (THF/DMF). β-phase confirmation of PVDF PNCs is done by FTIR studies. It is observed that ZnO-G filler enhances the β-phase content in the PNCs. Non-doped PVDF and PNCs are further studied for rheological behavior under the shear rate of 1–100 s⁻¹. Doping of ZnO-G dopant to the PVDF matrix changes its discontinuous shear thickening (DST) behavior to continues shear thickening behavior (CST). Hydrocluster formation and their interaction with the dopant could be the reason for this striking DST to CST behavioral change. Strain amplitude sweep (10⁻³% -10%) oscillatory test reveals that the PNCs shows extended linear viscoelastic region with high elastic modulus and lower viscous modulus. Effective shear thickening behavior and strong elastic strength of these PNCs present their candidature for various fields including mechanical and soft body armor applications.     

Structural Aspects of P2-Type Na0.67Mn0.6Ni0.2Li0.2O2 (MNL) Stabilization by Lithium Defects as a Cathode Material for Sodium-Ion Batteries

A known strategy for improving the properties of layered oxide electrodes in sodium-ion batteries is the partial substitution of transition metals by Li. Herein, the role of Li as a defect and its impact on sodium storage in P2-Na_0.67Mn_0.6Ni_0.2Li_0.2O₂ is discussed. In tandem with electrochemical studies, the electronic and atomic structure are studied using solid-state NMR, operando XRD, and density functional theory (DFT). For the as-synthesized material, Li is located in comparable amounts within the sodium and the transition metal oxide (TMO) layers. Desodiation leads to a redistribution of Li ions within the crystal lattice. During charging, Li ions from the Na layer first migrate to the TMO layer before reversing their course at low Na contents. There is little change in the lattice parameters during charging/discharging, indicating stabilization of the P2 structure. This leads to a solid-solution type storage mechanism (sloping voltage profile) and hence excellent cycle life with a capacity of 110 mAh g^-1 after 100 cycles. In contrast, the Li-free compositions Na_0.67Mn_0.6Ni_0.4O₂ and Na_0.67Mn_0.8Ni_0.2O₂ show phase transitions and a stair-case voltage profile. The capacity is found to originate from mainly Ni³⁺/Ni⁴⁺ and O^2-/O^2-δ redox processes by DFT, although a small contribution from Mn⁴⁺/Mn⁵⁺ to the capacity cannot be excluded.     

Synthesis of a Fe3O4-rGO-ZnO-catalyzed photo-Fenton system with enhanced photocatalytic performance

In this work, we designed a magnetically-separable Fe₃O₄-rGO-ZnO ternary catalyst, ZnO anchored on the surface of reduced graphene oxide (rGO)-wrapped Fe₃O₄ magnetic nanoparticles, where rGO, as an effective interlayer, can enhance the synergistic effect between ZnO and Fe₃O₄. The effects of three operational parameters, namely irradiation time, hydrogen peroxide dosage, and the catalyst dosage, on the photo-Fenton degradation of methylene blue and methyl orange were investigated. The results showed that the Fe₃O₄-rGO-ZnO had great potential for the destruction of organic compounds from wastewater using the Fenton chemical oxidation method at neutral pH. Repeatability of the photocatalytic activity after 5 cycles showed only a tiny drop in the catalytic efficiency.     

CuxNi1-xO nanostructures and their nanocomposites with reduced graphene oxide: Synthesis,characterization, and photocatalytic applications

NiO nanostructure was synthesized using a simple co-precipitation method and was embedded on reduced graphene oxide surface via ultrasonication. Structural investigations were made through X-ray diffraction (XRD) and functional groups were confirmed by Fourier transform infrared spectroscopy (FTIR). XRD analysis revealed the grain size reduction with doping. Fourier transform infrared spectroscopy confirmed the presence of metal-oxygen bond in pristine and doped NiO nanostructure as well as the presence of carbon containing groups. Scanning electron microscopy (SEM) indicated that the particle size decreased when NiO nanostructure was doped with copper. BET surface area was found to increase almost up to 43 m²/g for Cu doped NiO nanostructure/rGO composite. Current-voltage measurements were performed using two probe method. UV–Visible spectroscopic profiles showed the blue and red shift for Cu doped NiO nanostructure and Cu doped NiO Nanostructure/rGO composite respectively. Rate constant for Cu doped NiO nanostructure/rGO composite found to increase 4.4 times than pristine NiO nanostructure.     

Synthesis of manganese titanate and its precursors from xerogel

An overview of research on the synthesis of manganese titanates is presented. The xerogel of Mn–Ti–O–C–H composition was synthesized from manganese acetate and titanium tetrabutylate via liquid-phase method using organic solvents. The calcination of xerogel in air at 450 °C and 700 °C yielded manganese titanate precursors in the form of a nanostructured mixture of Mn₂O₃ and TiO₂. Annealing at 1000 °C, manganese metatitanate MnTiO₃ was obtained. Reference experiments with initial reagents included, separately, thermal decomposition of Mn(CH₃COO)₂×4H₂O and the product of Ti(OC₄H₉)₄ hydrolysis. The composition, structure, and properties of the products were studied using X-ray diffraction, scanning electron microscopy, elemental analysis, diffuse reflectance IR Fourier spectroscopy, thermogravimetry, and by measuring specific surface area. The data presented by these different techniques are basically consistent with each other (with an increase in the annealing temperature, an increase in globule size and decrease in specific surface area are observed; structuring occurs within the long- and short-range order; the size of the crystallites does not exceed that of the globules; elemental composition correlates with phase composition; the endothermic character of the reaction of MnTiO₃ formation at 900 °C is confirmed by a thermodynamic calculation). Nevertheless, some unexpected effects were revealed (based on the FTIR diffuse reflection spectra, mixed oxide Mn–Ti–O is formed in the surface layer of particles already at 450 °C and 700 °C; etc.). Application of the proposed technique for modifying Al₂O₃ powders, with the aim of implementing low-temperature sintering of corundum ceramics, is discussed.     

Electrophoretic deposition of graphene oxide on carbon brush as bioanode for microbial fuel cell operated with real wastewater

Microbial fuel cell (MFC) is a promising technology for simultaneous wastewater treatment and energy harvesting. The properties of the anode material play a critical role in the performance of the MFC. In this study, graphene oxide was prepared by a modified hummer's method. A thin layer of graphene oxide was incorporated on the carbon brush using an electrophoretic technique. The deoxygenated graphene oxide formed on the surface of the carbon brush (RGO-CB) was investigated as a bio-anode in MFC operated with real wastewater. The performance of the MFC using the RGO-CB was compared with that using plain carbon brush anode (PCB). Results showed that electrophoretic deposition of graphene oxide on the surface of carbon brush significantly enhanced the performance of the MFC, where the power density increased more than 10 times (from 33 mWm^?2 to 381 mWm^?2). Although the COD removal was nearly similar for the two MFCs, i.e., with PCB and RGO-CB; the columbic efficiency significantly increased in the case of RGO-CB anode. The improved performance in the case of the modified electrode was related to the role of the graphene in improving the electron transfer from the microorganism to the anode surface, as confirmed from the electrochemical impedance spectroscopy measurements.     

Spray dryer processed graphene oxide/reduced graphene oxide for high-performance supercapacitor

This study deals with the utility of mini spray dryer process to improve the dispersibility, of graphene oxide(GO) and its application for high-performance supercapacitor. Initially, the neutral solution of GO was obtained using the modified Hummer's method. After this, the prepared GO solution was processed by mini spray dryer to obtain a more purified, lighter, and dispersed form of GO which is named as spray dryer processed GO (SPGO). The SPGO thus obtained showed excellent dispersibility behavior with various solvents, which is not found in case of conventional oven drying. Furthermore, utility of SPGO and its reduced form (r-SPGO) for supercapacitor applications have been investigated. Results obtained from the cyclic voltammetry(CV) analysis, impedance, and charge-discharge behavior of supercapacitor fabricated using r-SPGO shows enhanced features. Therefore, the simple spray dried GO and its reduced form, that is, r-SPGO can be utilized as a potential candidate for the supercapacitor application. Herein, as synthesized SPGO exhibited the specific capacitance of 12.07 and 37.6 F/g with PVA-H₃PO₄ and 1 mol/L H₃PO₄, respectively, at a scan rate of 5 mV/s. On the other hand, reduced form of SPGO, that is, r-SPGO showed the specific capacitance of 27.16 and 230 F/g with PVA-H₃PO₄ and 1 mol/L H₃PO₄, respectively.