Understanding the adsorptive interactions of arsenate-iron nanoparticles with curved fullerene-like sheets in activated carbon using a quantum mechanics/molecular mechanics computational approach.

The prevalence of global arsenic groundwater contamination has driven widespread research on developing effective treatment systems including adsorption using various sorbents. The uptake of arsenic-based contaminants onto established sorbents such as activated carbon (AC) can be effectively enhanced via immobilization/impregnation of iron-based elements on the porous AC surface. Recent suggestions that AC pores structurally consist of an eclectic mix of curved fullerene-like sheets may affect the arsenic adsorption dynamics within the AC pores and is further complicated by the presence of nano-sized iron-based elements. We have therefore, attempted to shed light on the adsorptive interactions of arsenate-iron nanoparticles with curved fullerene-like sheets by using hybridized quantum mechanics/molecular mechanics (QMMM) calculations and microscopy characterization. It is found that, subsequent to optimization, chemisorption between HAsO42- and the AC carbon sheet (endothermic process) is virtually non-existent - this observation is supported by experimental results. Conversely, the incorporation of iron nanoparticles (FeNPs) into the AC carbon sheet greatly facilitates chemisorption of HAsO42-. Our calculation implies that iron carbide is formed at the junction between the iron and the AC interface and this tightly chemosorbed layer prevents detachment of the FeNPs on the AC surface. Other aspects including electronic structure/properties, carbon arrangement defects and rate of adsorptive interaction, which are determined using the Climbing-Image NEB method, are also discussed.

A simple procedure for the production of large ferromagnetic cobalt nanoparticles.

Epsilon cobalt (ε-Co) nanoparticles in a number of octahedral morphologies have been synthesised. The particles are polycrystalline, with sizes in the order of 30 nm. Magnetic studies reveal the particles are ferromagnetic, with a room temperature saturation magnetisation of 131 emu g(-1). Unlike other large cubic ε-Co syntheses, we have not added an additional co-surfactant. Instead, we have modified the heating regime and reaction agitation. This alternative method highlights the complex chemistry associated with the formation of cobalt nanoparticles by thermal decomposition.

Probing the interactions of phenol with oxygenated functional groups on curved fullerene-like sheets in activated carbon.

The mechanism(s) of interactions of phenol with oxygenated functional groups (OH, COO and COOH) in nanopores of activated carbon (AC) is a contentious issue among researchers. This mechanism is of particular interest because a better understanding of the role of such groups in nanopores would essentially translate to advances in AC production and use, especially in regard to the treatment of organic-based wastewaters. We therefore attempt to shed more light on the subject by employing density functional theory (DFT) calculations in which fullerene-like models integrating convex or concave structure, which simulate the eclectic porous structures on AC surface, are adopted. TEM analysis, EDS mapping and Boehm titration are also conducted on actual phenol-adsorbed AC. Our results suggest the widely-reported phenomenon of decreased phenol uptake on AC due to increased concentration of oxygenated functional groups is possibly attributed to the increased presence of the latter on the convex side of the curved carbon sheets. Such a system effectively inhibits phenol from getting direct contact with the carbon sheet, thus constraining any available π-π interaction, while the effect of groups acting on the concave part of the curved sheet does not impart the same detriment.

New Insights into the adsorption of aurocyanide ion on activated carbon surface: electron microscopy analysis and computational studies using fullerene-like models.

Despite decades of concerted experimental studies dedicated to providing fundamental insights into the adsorption of aurocyanide ion, Au(CN)2(-), on activated carbon (AC) surface, such a mechanism is still poorly understood and remains a contentious issue. This adsorption process is an essential unit operation for extracting gold from ores using carbon-in-pulp (CIP) technology. We hereby attempt to shed more light on the subject by employing a range of transmission electron microscopy (TEM) associated techniques. Gold-based clusters on the AC surface are observed by Z-contrast scanning TEM imaging and energy-filtered TEM element mapping and are supported by X-ray microanalysis. Density functional theory (DFT) calculations are applied to investigate this adsorption process for the first time. Fullerene-like models incorporating convex, concave, or planar structure which mimic the eclectic porous structures on the AC surface are adopted. Pentagonal, hexagonal, and heptagonal arrangements of carbon rings are duly considered in the DFT study. By determining the favored adsorption sites in water environment, a general adsorption trend of Au(CN)2(-) adsorbed on AC surface is revealed whereby concave > convex ≈ planar. The results suggest a tendency for Au(CN)2(-) ion to adsorb on the carbon sheet defects or edges rather than on the basal plane. In addition, we show that the adsorption energy of Au(CN)2(-) is approximately 5 times higher than that of OH(-) in the alkaline environment (in negative ion form), compared to only about 2 times in acidic environment (in protonated form), indicating the Au extraction process is much favored in basic condition. The overall simulation results resolve certain ambiguities about the adsorption process for earlier studies. Our findings afford crucial information which could assist in enhancing our fundamental understanding of the CIP adsorption process.

Filling the voids of graphene foam with graphene "eggshell" for improved lithium-ion storage.

Highly porous, N-doped graphene foam is synthesized by chemical vapor deposition process on nickel foam. The voids of the graphene foam can be filled with curved graphene sheets by impregnating the nickel foam template with micrometer-sized nickel powder. Subsequent etching of nickel produces a graphene "eggshells"-in-graphene foam structure. The reversible capacity of such graphene foam when used as anode in lithium ion battery is improved by the presence of graphene "eggshells", as compared to the unfilled foam. The improvement is attributed to the higher rate of lithium diffusion, better buffering of strain associated with lithiation/delithiation and higher volumetric energy density of the unique eggshell-in-graphene foam structure.

Graphene as atomic template and structural scaffold in the synthesis of graphene-organic hybrid wire with photovoltaic properties.

The dual role of graphene (or reduced graphene oxide) as atomic template and structural scaffold in the nucleation and assembly of organic nanostructures is demonstrated. The π-π stacking interactions between graphene and aromatic organic molecules affords synergistic binding interactions, with the host and guest assuming the interchangeable roles of atomic template and structural scaffold. Beginning with the seeding of organic wires on graphene template, the outgrown organic wires in turn act as one-dimensional scaffolds where graphene sheets coat around to form a unique graphene-organic hybrid structure. Using this π-assembly approach, we have synthesized one-dimensional hybrid structures consisting of graphene-N,N'-dioctyl-3,4,9,10-perylenedicarboximide (PDI) organic wires. This hybrid structure shows enhanced performance over its individual components in donor-acceptor type (PDI-Graphene/polythiophene) solar cells.

Transient photoconductivity and femtosecond nonlinear optical properties of a conjugated polymer-graphene oxide composite.

A water soluble conjugated thiophene polymer, sodium salt of poly[2-(3-thienyl)ethoxy-4-butylsulfonate] (TPP), and graphene oxide (GO) composite film (GO-TPP) device was prepared. Transient photoconductivity measurements were carried out on the GO-TPP composite film using 150 ns laser pulses of 527 nm wavelength. Highly efficient photocurrent generation was observed from the GO-TPP film. The relationships of the film photoconductivity, photocurrent decay time and electron decay times with the incident light intensity were investigated. The photoconductive gain of the film was determined to be greater than 40% and to be independent of the light intensity. Furthermore, the femtosecond nonlinear optical properties of the GO-TPP film were measured using 800 nm femtosecond laser pulses and the composite film exhibited high nonlinear absorption and nonlinear refraction coefficients.

Room-temperature synthesis of soluble carbon nanotubes by the sonication of graphene oxide nanosheets.

The transformation of two-dimensional graphene oxide (GO) nanosheets into carbon nanotubes was achieved by sonicating GO in 70% nitric acid. Through the use of mass spectrometry to track the evolution of molecular fragments during the acid ultrasonication, it was observed that GO can be readily decomposed into polyaromatic hydrocarbons (PAHs). The cavitation-induced condensation of these PAHs results in their molecular reconstruction to form folded carbon nanostructures. UV-emitting, water-soluble carbon nanoparticles as well as carbon nanotubes that exhibit magnetic properties were fabricated under catalyst-free conditions.