Harnessing bio-based chelating agents for sustainable synthesis of AgNPs: Evaluating their inherent attributes and antimicrobial potency in conjunction with honey.

Greenly synthesized nanoparticles have garnered attention due to their low environmental footprint, but impurities limit their applications. A novel semi-organic method for synthesizing silver nanoparticles (AgNPs) using bio-based chelating fuels (Beta vulgaris subsp., Spinacia oleracea, and Ipomoea batatas) reduces the undesirable impurities. The study also showcases the impact of bio-based chelating fuel on various characteristics of AgNPs in comparison to synthetic chelating fuel. The antimicrobial efficacy of the synthesized AgNPs in conjunction with honey was also assessed against E. coli. The XRD analysis showed cubic structure of AgNPs. The FESEM and TEM analysis showed that the well-connected spherical-shaped AgNPs (∼3-120 nm diameter) while EDS confirmed the presence of Ag in all samples. The TEM analysis also revealed layers of carbonates in AgNPs synthesized using bio-based chelating fuels. XPS investigation confirmed the absence of any prominent impurities in prepared samples and AgNPs have not experienced oxidation on their surface. However, notable surface charging effects due to the uneven conductivity of the particles were observed. The broth dilution method showed that all mixtures containing AgNPs in combination with honey exhibited a significant bacterial growth reduction over a period of 120 h. The highest growth reduction of ∼75 % is obtained for the mixture having AgNPs (Ipomoea batatas) while the least growth reduction of ∼51 % is obtained for the mixture having AgNPs (Beta vulgaris subsp.). The findings affirm that AgNPs can be successfully synthesized using bio-based chelating fuels with negligible ecological consequences and devoid of contaminants. Moreover, the synthesized AgNPs can be employed in conjunction with honey for antibacterial purposes.

Sequestration of an Azo Dye by a Potential Biosorbent: Characterization of Biosorbent, Adsorption Isotherm and Adsorption Kinetic Studies.

This study explores the detailed characterization of a biosorbent (Hen Feather) and its efficient use in eradicating the azo dye Metanil Yellow (MY) from its aqueous solutions. Effects of a range of experimental parameters, including pH, initial dye concentration, biosorbent dosage and contact time on the adsorption, were studied. A detailed physical and chemical characterization of the biosorbent was made using SEM, XRD, XPS and FTIR. During the optimization of adsorption parameters, the highest dye uptake of almost 99% was recorded at pH 2, dye concentration 2 × 10-5 M, 0.05 g of biosorbent and a contact period of 75 min. Various adsorption isotherm models were studied to gather different adsorption and thermodynamic parameters. The linearity of the Langmuir, Freundlich and D-R adsorption isotherms indicate homogeneous, multilayer chemisorption with high adsorption affinity between the dye and biosorbent. Values of the changes in the Gibbs free energy (ΔG°) and the enthalpy (ΔH°) of the adsorption process have been calculated, these values indicate that it is a spontaneous and endothermic process. Kinetics of the adsorption were also measured, and it was established that the adsorption of MY over Hen Feather follows a pseudo-second-order kinetic model at temperatures 30, 40 and 50 °C. The findings of this investigation clearly indicate that the studied biosorbent exhibits a high affinity towards the dye (MY), and it can be effectively, economically and efficiently used to sequestrate and eradicate MY from its aqueous solutions.

Ordered Mesoporous Ceria and Cerium Gadolinium Oxide Prepared by Vacuum-Assisted Nanocasting.

Four ceria-based mesoporous oxide materials were prepared using a new vacuum impregnation (VI) templating method developed by the authors, namely, vacuum-assisted nanocasting (VAN). Two hard templates (SBA-15 and KIT-6) were employed, and products with compositions CeO2 and Ce0.9Gd0.1O1.9 (CGO) were made with each. The desired fluorite phase and composition were confirmed by powder XRD and EDS. The product structures were characterised by XRD, TEM, gas physisorption and SAXS. All products contained ordered mesoporous material in high yields. The specific surface areas (SSAs) and pore volumes of the products were determined to be high and the pore size and pore spacings related well to the templates from which the materials were synthesised. The TEM studies confirmed that the samples had a 3D pore structure, with this being the negative of the original template. The target materials were not only produced in high yields, but also displayed a porous single-crystal morphology with non-linear lattice planes. The highest SSA values and pore volumes were reported for materials impregnated using the KIT-6 template and with the CGO composition. The results suggest that VAN is an excellent and reproducible method for producing ordered mesoporous cerias and has considerable potential for wider application. All the mesoporous products showed dramatically increased reducibility in TPR experiments compared with a high-SSA nanoparticulate ceria reference. This is very promising for their potential applications in oxidation catalysts and in fuel cell components.

Nanostructured carbons containing FeNi/NiFe2O4 supported over N-doped carbon nanofibers for oxygen reduction and evolution reactions.

Non-precious metal-based electrocatalysts on carbon materials with high durability and low cost have been developed to ameliorate the oxygen-reduction reaction (ORR) and oxygen-evolution reaction (OER) for electrochemical energy applications such as in fuel cells and water electrolysis. Herein, two different morphologies of FeNi/NiFe2O4 supported over hierarchical N-doped carbons were achieved via carbonization of the polymer nanofibers by controlling the ratio of metal salts to melamine: a mixture of carbon nanotubes (CNTs) and graphene nanotubes (GNTs) supported over carbon nanofibers (CNFs) with spherical FeNi encapsulated at the tips (G/CNT@NCNF, 1 : 3), and graphene sheets wrapped CNFs with embedded needle-like FeNi (GS@NCNF, 2 : 3). G/CNT@NCNF shows excellent ORR activity (on-set potential: 0.948 V vs. RHE) and methanol tolerance, whilst GS@NCNF exhibited significantly lower over-potential of only 230 mV at 10 mA cm-2 for OER. Such high activities are due to the synergistic effects of bimetallic NPs encapsulated at CNT tips and N-doped carbons with unique hierarchical structures and the desired defects.

Synthesis of mesoporous ceria using metal- and halogen-free ordered mesoporous carbon as a hard template.

Ordered mesoporous cerias were synthesised by employing metal- and halogen-free ordered mesoporous carbons (OMCs) as the hard templates in a 'nanocasting' procedure. TEM, small angle (SA) and wide angle (WA) XRD, and N2 physisorption analyses were used to characterise the templates, intermediates and ceria products and electron tomography (STEM-HAADF) was used to explore the 3D morphology of the ceria nanostructures grown within the carbon templates. This allowed the relationships between the structures of the OMC templates and the products to be considered in detail as two parameters were varied. These were: the method of impregnation of the ceria precursor; and the temperature of calcination of the OMC template. Of the four impregnation methods tested, the solid-liquid method was found to be the most successful. This gave a high quality product with the highest yield of uniform mesopores, and crystalline nanorods of ceria arrayed in clear long-range order, as viewed by TEM and determined in SA and WAXRD. The specific surface area and pore volume exhibited by this sample were 111 m2 g-1 and 0.39 cm3 g-1, respectively. 3D electron tomography reconstructions revealed the presence of a network of ordered, nanoscale, rod-like structures interlinked in a complex fashion. The effect of calcination temperature of the template on uptake of the ceria precursor during impregnation was studied by calcining OMCs at temperatures from 350 to 800 °C and using these as hard templates for the nanocasting of ceria. Of these, the carbon template calcined at 400 °C gave the highest quality product.

Acetylene hydrogenation over structured Au-Pd catalysts.

AuPd nanoparticles were prepared following a methodology designed to produce core-shell structures (an Au core and a Pd shell). Characterisation suggested that slow addition of the shell metal favoured deposition onto the pre-formed core, whereas more rapid addition favoured the formation of a monometallic Pd phase in addition to some nanoparticles with the core-shell morphology. When used for the selective hydrogenation of acetylene, samples that possessed monometallic Pd particles favoured over-hydrogenation to form ethane. A sample prepared by the slow addition of a small amount of Pd resulted in the formation of a core-shell structure but with an incomplete Pd shell layer. This material exhibited a completely different product selectivity with ethylene and oligomers forming as the major products as opposed to ethane. The improved performance was thought to be as a result of the absence of Pd particles, which are capable of forming a Pd-hydride phase, with enhanced oligomer selectivity associated with reaction on uncovered Au atoms.

Electromechanical behaviour of Nafion-based soft actuators.

Soft actuators based on Ionic Polymer-Metal Composites (IPMCs) are of considerable interest for applications in biomedical devices and robotics. In this work, thin commercial and thick laboratory-prepared Nafion membranes were made into model IPMC actuator devices by incorporation of Pt electrode layers. In extensive electromechanical tests the maximum average tip displacement and maximum force generated were recorded. The effect of amplitude and frequency of the applied voltage on both displacement and force was examined as were the effects of the origin of the Nafion membrane, the Pt loading, the structure of the electrode and the presence or absence of an Au overlayer. The cast samples generated much smaller displacements but much larger forces than the commercial Nafion samples. For all samples, displacement and force increased with increasing applied voltage, with increased number of Pt plating cycles and when an Au overlayer was present but decreased with increasing applied voltage frequency. Waveform analysis of applied voltage, current and force was performed by considering the capacitive nature of the IPMC actuators.

Time-resolved mapping of water diffusion coefficients in a working soft actuator device.

Diffusion-weighted imaging was employed to spatially map the distribution of the diffusion coefficient of water, D, in bare, water-soaked, Li(+)-exchanged, cast Nafion and in an ionic polymer-metal composite (IPMC) soft actuator element, prepared from this bare Nafion by impregnation with Pt electrodes. D was evaluated in two orthogonal directions: along one of the long dimensions of the sample (Dx) and through its thickness (Dz). D-maps of the IPMC element were obtained both in the absence of an applied potential and in situ during the application of a 3 V dc potential across the thickness of the sample. In the bare Nafion, D-maps showed uniform values of both Dx and Dz of about 6 x 10 (-10) m(2) s(-1). In the IPMC two effects were observed: (i) D at the electroded surfaces of the IPMC was higher than at the center of the sample; (ii) this difference was much greater in Dz than in Dx . Both effects were explained by the influence of the impregnated Pt electrodes on polymer structure. The D-maps in the electrochemical measurements showed high values of D (up to 8 x 10(-10) m(2) s(-1)) at the cathode and low values (from 1 x 10(-10) m(2) s(-1)) at the anode. This was explained in terms of the effect on the Nafion nanostructure of the forced electro-migration of Li(H2O)x(+) species toward the cathode.

In situ magnetic resonance imaging of electrically-induced water diffusion in a nafion ionic polymer film.

By deploying a functioning electrochemical cell inside a Magnetic Resonance Imaging (MRI) instrument, images of the electrically-induced diffusion of water through a Li+ ion-exchanged Nafion ionic polymer film in the form of two-dimensional maps of proton density and transverse relaxation time, T2, were generated and changes in these images over time and with respect to changes made to the applied potential were followed.