Bimetallic platinum–ruthenium nanoparticles immobilized on reduced graphene oxide-TiO2 (RGO-TiO2) support for ethanol electro oxidation in acidic media

The present work addresses the potentialities of Pt–Ru nanoparticles deposited on a graphene oxide (RGO) and TiO₂ composite support towards electrochemical oxidation of ethanol in acidic media relevant for fuel cell applications. To immobilize platinum–ruthenium bimetallic nanoparticles on to an RGO-TiO₂ nanohybrid support a simple solution-phase chemical reduction method is utilized. An examination using electron microscopy and energy dispersive X-ray spectroscopy (EDS) indicated that Pt–Ru particles of 4–8 nm in diameter are dispersed on RGO-TiO₂ composite support. The corresponding Pt–Ru/RGO-TiO₂ nanocomposite electrocatalyst was studied for the electrochemical oxidation of ethanol in acidic media. Compared to the commercial Pt–Ru/C and Pt/C catalysts, Pt–Ru/RGO-TiO₂ nanocomposite yields higher mass-specific activity of about 1.4 and 3.2 times, respectively towards ethanol oxidation reaction (EOR). The synergistic boosting provided by RGO-TiO₂ composite support and Pt–Ru ensemble together contributed to the observed higher EOR activity and stability to Pt–Ru/RGO-TiO₂ nanocomposite compared with other in-house synthesized Pt–Ru/RGO, Pt/RGO and commercial Pt–Ru/C and Pt/C electrocatalysts. Further optimization of RGO-TiO₂ composite support provides opportunity to deposit many other types of metallic nanoparticles onto it for fuel cell electrocatalysis applications.     

1D sub 10 nm nanofabrication of ultrahydrophobic Ag@TiO2 nanowires and their photocatalytic,UV shielding and antibacterial properties

Here we report the synthesis of 1D TiO₂ sub 10 nm nanowires through one pot hydrothermal method in an alkaline NaOH medium at 95 °C for 36 h. Further, these TiO₂ nanowires were embellished with silver (Ag) using polyvinylpyrrolidone (PVP) and ethylene glycol (EG) based solvothermal route at 160 °C for 4 h. With Ag decoration the photocatalytic activity was enhanced and the complete photooxidation of Methylene Blue (MB) was achieved in 35 min under optimized conditions. Super- and ultra-hydrophobic coating on cotton fabric exhibited a consistent antibacterial activity with enhanced UV-blocking property. Enhanced multifunctional properties observed were primarily attributed to the formation of Ag decorated 1D sub 10 nm TiO₂ nanowires heterojunctions achieved using facile chemical route. Hence, such multiple functionalities make the 1D sub 10 nm TiO₂ nanowires good candidate for industrial and domestic wastewater treatment.     

Nano fibrillated cellulose-based foam by Pickering emulsion: Preparation,characterizations, and application as dye adsorbent

An ecofriendly and biodegradable porous structure was prepared from drying aqueous foams based on nano fibrillated cellulose (NFC), extracted from softwood pulp by subcritical water/CO₂ treatment (SC-NFC). The primary aim of this work was to use the modified SC-NFC as stabilizer for a water-based Pickering emulsion which upon drying, yielded porous cellulosic materials, a good dye adsorbent. In order to exploit the carboxymethylated SC-NFC (CMSC-NFC, with a degree of substitution of 0.35 and a charge density of 649 μeqv/g) as a stabilizer for water-based Pickering emulsion in subsequent step, an optimized quantity of octyl amine (30 mg/g of SC-NFC) was added to make them partially hydrophobic. A series of dry foam structures were prepared by varying the concentrations of treated CMSC-NFCs and 4 wt% was found to be the optimum concentration to yield foam with high porosity (99%) and low density (0.038 g/cc) along with high compression strength (0.24 MPa), superior to the conventionally extracted NFC. The foams were applied to capture as high as 98% of methylene blue dyes, making them a potential green candidate for treating industrial effluent. In addition, the dye adsorption kinetics and isotherms were found to be well suited with second order kinetics and Langmuir isotherm models.     

Thermal transport and chemical conversion in single reacting sorbent particles

The effects of particle size and carbon dioxide concentration on chemical conversion in engineered spherical particles undergoing calcium oxide looping are investigated. Particles are thermochemically cycled in a furnace under different carbon dioxide concentrations. Changes in composition due to chemical reactions are measured using thermogravimetric analysis. Gas composition at the furnace exit is evaluated with mass spectroscopy. A numerical model of thermal transport phenomena developed previously is adapted to match the physical system investigated in the present study. The model is used to elucidate effects of reacting medium characteristics on particle temperature and reaction extent. Experimental and numerical results show that (1) an increase in particle size results in a decrease in carbonation extent, and (2) the carbonation step consists of fast and slow reaction regimes. The reaction rates in the fast and slow carbonation regimes increase with increasing carbon dioxide concentration. The effect of carbon dioxide concentration and the distinction between the fast and slow regimes become more pronounced with increasing particle size.     

Engineering Silver-Enriched Copper Core-Shell Electrocatalysts to Enhance the Production of Ethylene and C2+ Chemicals from Carbon Dioxide at Low Cell Potentials

Copper catalysts are widely studied for the electroreduction of carbon dioxide (CO₂) to value-added hydrocarbon products. Controlling the surface composition of copper nanomaterials may provide the electronic and structural properties necessary for carbon-carbon coupling, thus increasing the Faradaic efficiency (FE) towards ethylene and other multi-carbon (C₂₊) products. Synthesis and catalytic study of silver-coated copper nanoparticles (Cu@Ag NPs) for the reduction of CO₂ are presented. Bimetallic CuAg NPs are typically difficult to produce due to the bulk immiscibility between these two metals. Slow injection of the silver precursor, concentrations of organic capping agents, and gas environment proved critical to control the size and metal distribution of the Cu@Ag NPs. The optimized Cu@Ag electrocatalyst exhibited a very low onset cell potential of −2.25 V for ethylene formation, reaching a FE towards C₂₊ products (FE_C2+) of 43% at −2.50 V, which is 1.0 V lower than a reference Cu catalyst to reach a similar FE_C2+. The high ethylene formation at low potentials is attributed to enhanced C C coupling on the Ag enriched shell of the Cu@Ag electrocatalysts. This study offers a new catalyst design towards increasing the efficiency for the electroreduction of CO₂ to value-added chemicals.     

Novel polymer composites of RuO2@nBaTiO3/PVDF with a high dielectric constant

The dielectric properties of a novel polymer dielectric material were investigated. The conductive phase of RuO₂ was synthesized for deposition on the surface of a nanosized BaTiO₃ (nBT). The RuO₂@nBT hybrid particles were incorporated into a poly (vinylidene fluoride) (PVDF) as a three-phase composite (RuO₂@nBT/PVDF). The obtained dielectric constant (ε′) was significantly high (3837.16) for the composite with a volume fraction of $f_{Ru{O}_2@nBT}$ = 0.50. The large interfacial polarization between the RuO₂?nBT and RuO₂?PVDF interfaces considerably increased the value of ε′. Therefore, interfacial polarization is a critical factor in improving the dielectric properties. The dielectric behavior of the RuO₂@nBT/PVDF composites can be described using the effective medium percolation theory model, which indicates the significant contributions of the conductive RuO₂ phase and high-permittivity nBT phase.     

Crystalline phase of TiO2 nanotube arrays on Ti–35Nb–4Zr alloy: Surface roughness,electrochemical behavior and cellular response

An investigation was made into the electrochemical, structural and biological properties of self-organized amorphous and anatase/rutile titanium dioxide (TiO₂) nanotubes deposited on Ti–35Nb–4Zr alloy through anodization-induced surface modification. The surface of as-anodized and heat-treated TiO₂ nanotubes was analyzed by field emission scanning electron microscopy (FE-SEM), revealing morphological parameters such as tube diameter, wall thickness and cross-sectional length. Glancing angle X-ray diffraction (GAXRD) was employed to identify the structural phases of titanium dioxide, while atomic force microscopy (AFM) was used to measure surface roughness associated with cell interaction properties. The electrochemical stability of TiO₂ was examined by electrochemical impedance spectroscopy (EIS) and the results obtained were correlated with the microstructural characterization. The in vitro bioactivity of as-anodized and crystallized TiO₂ nanotubes was also analyzed as a function of the presence of different TiO₂ polymorphic phases. The results indicated that anatase TiO₂ showed higher surface corrosion resistance and greater cell viability than amorphous TiO₂, confirming that TiO₂ nanotube crystallization plays an important role in the material's electrochemical behavior and biocompatibility.