Active Site Engineering and Theoretical Aspects of "Superhydrophilic" Nanostructure Array Enabling Efficient Overall Water Electrolysis.

The rational design of noble metal-free electrocatalysts holds great promise for cost-effective green hydrogen generation through water electrolysis. In this context, here, the development of a superhydrophilic bifunctional electrocatalyst that facilitates both oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in alkaline conditions is demonstrated. This is achieved through the in situ growth of hierarchical NiMoO4 @CoMoO4 ·xH2 O nanostructure on nickel foam (NF) via a two-step hydrothermal synthesis method. NiMoO4 @CoMoO4 ·xH2 O/NF facilitates OER and HER at the overpotentials of 180 and 220 mV, respectively, at the current density of 10 mA cm-2 . The NiMoO4 @CoMoO4 ·xH2 O/NF ǁ NiMoO4 @CoMoO4 ·xH2 O/NF cell can be operated at a potential of 1.60 V compared to 1.63 V displayed by the system based on the Pt/C@NFǁRuO2 @NF standard electrode pair configuration at 10 mA cm-2 for overall water splitting. The density functional theory calculations for the OER process elucidate that the lowest ΔG of NiMoO4 @CoMoO4 compared to both Ni and NiMoO4 is due to the presence of Co in the OER catalytic site and its synergistic interaction with NiMoO4 . The preparative strategy and mechanistic understanding make the windows open for the large-scale production of the robust and less expensive electrode material for the overall water electrolysis.

Hierarchical Nanoflower Arrays of Co9 S8 -Ni3 S2 on Nickel Foam: A Highly Efficient Binder-Free Electrocatalyst for Overall Water Splitting.

Hydrogen production is vital for meeting future energy demands and managing environmental sustainability. Electrolysis of water is considered as the suitable method for H2 generation in a carbon-free pathway. Herein, the synthesis of highly efficient Co9 S8 -Ni3 S2 based hierarchical nanoflower arrays on nickel foam (NF) is explored through the one-pot hydrothermal method (Co9 S8 -Ni3 S2 /NF) for overall water splitting applications. The nanoflower arrays are self-supported on the NF without any binder, possessing the required porosity and structural characteristics. The obtained Co9 S8 -Ni3 S2 /NF displays high hydrogen evolution reaction (HER), as well as oxygen evolution reaction (OER), activities in 1 m KOH solution. The overpotentials exhibited by this system at 25 mA cm-2 are nearly 277 and 102 mV for HER and OER, respectively, in 1 m KOH solution. Subsequently, the overall water splitting was performed in 1 m KOH solution by employing Co9 S8 -Ni3 S2 /NF as both the anode and cathode, where the system required only 1.49, 1.60, and 1.69 V to deliver the current densities of 10, 25, and 50 mA cm-2 , respectively. Comparison of the activity of Co9 S8 -Ni3 S2 /NF with the state-of-the-art Pt/C and RuO2 coated on NF displays an enhanced performance for Co9 S8 -Ni3 S2 /NF both in the half-cell as well as in the full cell, emphasizing the significance of the present work. The post analysis of the material after water electrolysis confirms that the surface Co(OH)2 formed during the course of the reaction serves as the favorable active sites. Overall, the activity modulation achieved in the present case is attributed to the presence of the open-pore morphology of the as formed nanoflowers of Co9 S8 -Ni3 S2 on NF and the simultaneous presence of the surface Co(OH)2 along with the highly conducting Co9 S8 -Ni3 S2 core, which facilitates the adsorption of the reactants and subsequently its conversion into the gaseous products during water electrolysis.

Micro-structural analysis of NiFe2O4 nanoparticles synthesized by thermal plasma route and its suitability for BSA adsorption.

The paper presents the experimental studies pertaining to the adsorption of bovine serum albumin (BSA) on the nanoparticles of nickel ferrite (NiFe2O4) with a view of correlating the adsorption properties to their microstructure and zeta potentials. Physical properties of two kinds of nickel ferrites, one synthesized by thermal plasma route and the other by chemical co-precipitation method, are compared. Maximum adsorption (231.57 µg/mg) of BSA onto nickel ferrite nanoparticles, at body temperature (37 °C) was observed at pH-value of 5.58 for the thermal plasma synthesized particles showing its higher adsorption capacity than those synthesized by wet chemical means (178.71 µg/mg). Under the same physical conditions the value of zeta potential, obtained for the former, was higher than that of the latter over a wide range of pH values (3.64-9.66). This is attributed to the differences in the specific surface energies of the two kinds of nanoparticles arising from the degree of crystallinity. The paper presents the experimental evidence for the single crystalline nature of the individual nanoparticles, with mean size of 32 nm, for the thermal plasma synthesized particles as evidenced from the high resolution transmission electron microscopy and electron diffraction analysis. The measurements also reveal the poor crystalline morphology in the chemically prepared particles (mean size of 28 nm) although the X-ray diffraction patterns are not much different. The atomic force microscopy images confirm that the surfaces of plasma synthesized nanoparticles possesses higher surface roughness than that of chemically synthesized one. Presence of adsorbed protein was confirmed by vibrational spectroscopy. The Langmuir adsorption model is found to fit into the experimental data better than the Freundlich adsorption model.

Phase behavior of lipid-based lyotropic liquid crystals in presence of colloidal nanoparticles.

We have investigated the microstructure and phase behavior of monoglyceride-based lyotropic liquid crystals in the presence of hydrophilic silica colloidal particles of size comparable to or slightly exceeding the repeat units of the different liquid crystalline phases. Using small angle X-ray scattering (SAXS) and differential scanning calorimetry (DSC), we compare the structural properties of the neat mesophases with those of the systems containing silica colloidal particles. It is found that the colloidal particles always macrophase separate in inverse bicontinuous cubic phases of gyroid (Ia3d) and double diamond (Pn3m) symmetries. SAXS data for the inverse columnar hexagonal phase (H(II)) and lamellar phase (L(α)) suggest that a low volume fraction of the nanoparticles can be accommodated within the mesophases, but that at concentrations above a given threshold, the particles do macrophase separate also in these systems. The behavior is interpreted in terms of the enthalpic and entropic interactions of the nanoparticles with the lamellar and hexagonal phases, and we propose that, in the low concentration limit, the nanoparticles are acting as point defects within the mesophases and, upon further increase in concentration, initiate nucleation of nanoparticles clusters, leading to a macroscopic phase separation.

Alternating electric-field-induced assembly of binary mixtures of soft repulsive ionic microgel colloids.

An external alternating electric field is used to study the assembly of a binary mixture of Poly(N-isopropylacrylamide-co-acrylic acid) microgels in their swollen form at hydrodynamic size ratio 2:1 under deprotonated state. The AC field experiments were carried out at a fixed frequency of 100 kHz in the fluid regime for three number density ratios 1:3, 1:1 and 3:1 of big-to-small microgels using a confocal microscope. Strings with different types of co-assembly structures such as buckled, ring, flame and sandwich have been observed at low and intermediate field strengths at ratio 1:3, 1:1. In buckled and ring type, one or two small particles sit at the contact of two big particles and in the flame type, small particles arrange like a cone at end of the string. In the sandwich structure, several double small particle layers lie in between big particles. At high field strength, aggregation of strings and a phase separation into individual aggregates of strings from both big and small microgels have been observed. At higher ratio 3:1, the string formation is mostly dominated by big particles. Our experimental results are discussed with the recent simulation and experimental works on AC field induced structures in binary hard sphere mixtures.

Room-Temperature Activation of CO2 by Dual Defect-Stabilized Nanoscale Hematite (Fe2-δO3-v ): Concurrent Role of Fe and O Vacancies.

We demonstrate that synthetically controlled concurrent stabilization of Fe and O vacancy defects on the surface of interbraided nanoscale hematite (Fe2-δO3-v ) renders an interesting surface chemistry which can reduce CO2 to CO at room temperature (RT). Importantly, we realized a highly enhanced output of 410 µmol h-1 g-1 at RT, as compared to that of 10 µmol h-1 g-1 for bulk hematite. It is argued based on the activity degradation under cycling and first principles density functional theory calculations that the excess chemical energy embedded in the defect-stabilized surface is expended in this high-energy conversion process, which leads to progressive filling up of oxygen vacancies.

Template-Free Assembly in Living Bacterial Suspension under an External Electric Field.

Although template-assisted self-assembly methods are very popular in materials and biological systems, they have certain limitations such as lack of tunability and switchable functionality because of the irreversible association of cells and their matrix components. With an aim to achieve more tunability, we have made an attempt to investigate the self-assembly behavior of rod-shaped living bacteria subjected to an external alternating electric field using confocal microscopy. We demonstrate that rod-shaped living bacteria dispersed in a low salinity aqueous medium form different types of reversible freely suspended structures when subjected to an external alternating electric field. At low field strength, an oriented phase is observed where individual bacterium orients with its major axis aligned along the field direction. At intermediate field strength, bacteria align in the form of one-dimensional (1D) chains that lie along the field direction. Further, at high field strength, more bacteria associate with these 1D chains laterally to form a two-dimensional (2D) array. At higher bacterial concentration, these field-induced 2D arrays extend to form three-dimensional columnar structures. These results are discussed in the context of previously reported studies on bacterial self-assembly.