Fullerene C60 sub-colloidal particle with diameter ∼1 nm represents a boundary case between small and large hydrophobic solutes on the length scale of hydrophobic hydration. In the present paper, a molecular dynamics simulation is performed to investigate this complex phenomenon for bare C60 fullerene and its amphiphilic/charged derivatives, so called shape amphiphiles. Since most of the unique properties of water originate from the pattern of hydrogen bond network and its dynamics, spatial, and orientational aspects of water in solvation shells around the solute surface having hydrophilic and hydrophobic regions are analyzed. Dynamical properties such as translational-rotational mobility, reorientational correlation and occupation time correlation functions of water molecules, and diffusion coefficients are also calculated. Slower dynamics of solvent molecules—water retardation—in the vicinity of the solutes is observed. Both the topological properties of hydrogen bond pattern and the "dangling" -OH groups that represent surface defects in water network are monitored. The fraction of such defect structures is increased near the hydrophobic cap of fullerenes. Some "dry" regions of C60 are observed which can be considered as signatures of surface dewetting. In an effort to provide molecular level insight into the thermodynamics of hydration, the free energy of solvation is determined for a family of fullerene particles using thermodynamic integration technique.

Porphyrin–graphene oxide frameworks for ambient temperature sodium-ion storage are investigated. The presence of porphyrin caters for a stronger sodium ion–electrode interaction to realize high-performance sodium-ion batteries, which deliver a capacity of ∼200 mA h g−1even after resting for one month.

We perform constant voltage Gibbs ensemble based grand canonical Monte Carlo simulations for nanosized supercapacitors comprising graphene slit electrodes in symmetric and asymmetric electrolytes. Our simulations demonstrate that external electrolyte at the electrode surface can be exploited to positively influence the structure and packing of that inside the slit, when the system is engineered to allow these to interact. Oscillatory dependence of capacitance on slit-pore size, seen in recent results from molecular dynamics simulation and density functional theory, is observed also in our Monte Carlo simulations. A detailed analysis suggests that maximum in capacitance occurs in subnanometre pores because of the interference between internal double layers (largely the Helmholtz parts) on the opposite sides of the slit, expelling the co-ions; and that the oscillatory character of capacitance with pore width is due to relative changes in counterion and co-ion populations with pore width, also dictated by the interference process between the two internal double layers. Our simulations with size-asymmetric and size-symmetric electrolytes with different sets of electrode pairs reveal that when the pore widths of both the electrodes are close to their respective counterion sizes, the electrodes store maximum charge density, yielding maximum capacitance. Thus, it is demonstrated that for asymmetric electrolytes optimum capacitance is obtained using a correspondingly asymmetric electrode combination.

Water displays anomalous fast diffusion in narrow carbon nanotubes (CNTs), a behavior that has been reproduced in both experimental and simulation studies. However, little is reported on the effect of bulk water-CNT interfaces, which is critical to exploiting the fast transport of water across narrow carbon nanotubes in actual applications. Using molecular dynamics simulations, we investigate here the effect of such interfaces on the transport of water across arm-chair CNTs of different diameters. Our results demonstrate that diffusion of water is significantly retarded in narrow CNTs due to bulk regions near the pore entrance. The slowdown of dynamics can be attributed to the presence of large energy barriers at bulk water-CNT interfaces. The presence of such intense barriers at the bulk-CNT interface arises due to the entropy contrast between the bulk and confined regions, with water molecules undergoing high translational and rotational entropy gain on entering from the bulk to the CNT interior. The intensity of such energy barriers decreases with increase in CNT diameter. These results are very important for emerging technological applications of CNTs and other nanoscale materials, such as in nanofluidics, water purification, nanofiltration, and desalination, as well as for biological transport processes.

Sodium ion storage in reduced graphene oxide, Electrochimica Acta http://dx.doi.org/10. 1016/j.electacta.2016.08.058 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. AbstractThe performance of few-layered metal-reduced graphene oxide (RGO) as a negative electrode material in sodium-ion battery was investigated. Experimental and simulation results indicated that the as-prepared RGO with a large interlayer spacing and disordered structure enabled significant sodium-ion storage, leading to a high discharge capacity. The strong surface driven interactions between sodium ions and oxygen-containing groups and/or defect sites led to a high rate performance and cycling stability. The RGO anode delivered a discharge capacity of 272 mA h g -1 at a current density of 50 mA g -1 , a good cycling stability over 300 cycles and a superior rate capability. The present work provides new insights into optimizing RGOs for high-performance and low-cost sodium-ion batteries.

We illustrate here the interplay of decoordination and accessible pore volume in nanosized supercapacitors, using constant voltage Gibbs ensemble based grand canonical Monte Carlo simulations for three different microporous carbon electrodes of known atomistic structure and 1-ethyl-3methylimidazolium boron tetrafluoride (EMI-BF 4 ) as electrolyte. We demonstrate that the counterion coordination number decreases with pore size, and this trend is similar for the electrodes considered, despite their different structures, suggesting that the pore shape is less important to this relation, at least for the carbons examined here. It is seen that ions with low coordination and/or completely decoordinated ions induce maximum charge, while those with higher coordination induce less, in accordance with recent MD simulation results which demonstrate that ions in high degree of confinement (DOC) induce more charge than those in low DOC. Our results indicate that electrodes with different pore volumes can exhibit similar capacitances by balancing accessibility and decoordination effects. Thus, similar capacitance may be obtained for electrodes having low pore volume, but which can adsorb a small amount of high charge inducers (decoordinated ions) by virtue of having suitable pore size, and those having high pore volume and adsorbing many more low charge inducers (more highly coordinated ions).

A molecular dynamics (MD) investigation of LiCl in water, methanol, and ethylene glycol (EG) at 298 K is reported. Several structural and dynamical properties of the ions as well as the solvent such as self-diffusivity, radial distribution functions, void and neck distributions, velocity autocorrelation functions, and mean residence times of solvent in the first solvation shell have been computed. The results show that the reciprocal relationship between the self-diffusivity of the ions and the viscosity is valid in almost all solvents with the exception of water. From an analysis of radial distribution functions and coordination numbers the nature of hydrogen bonding within the solvent and its influence on the void and neck distribution becomes evident. It is seen that the solvent−solvent interaction is important in EG while solute−solvent interactions dominate in water and methanol. From Voronoi tessellation, it is seen that the voids and necks within methanol are larger as compared to those within water or EG. On the basis of the void and neck distributions obtained from MD simulations and literature experimental data of limiting ion conductivity for various ions of different sizes, we show that there is a relation between the void and neck radius on the one hand and dependence of conductivity on the ionic radius on the other. It is shown that the presence of large diameter voids and necks in methanol is responsible for maximum in limiting ion conductivity (λ0) of TMA+, while in water and EG, the maximum is seen for Rb+. In the case of monovalent anions, maximum in λ0 as a function ionic radius is seen for Br− in water and EG but for the larger ClO4 − ion in methanol. The relation between the void and neck distribution and the variation in λ0 with ionic radius arises via the Levitation effect which is discussed. These studies show the importance of the solvent structure and the associated void structure.

Extensive full-atomistic molecular dynamics simulations are performed to study the self-organization of C60-fullerene dyad molecules in water, namely phenyl-C61-butyric acid methyl ester and fulleropyrrolidines, which have two elements of ordering, the hydrophobic fullerene cage and the hydrophilic/ionic group. While pristine fullerene or phenyl-C61-butyric acid methyl ester forms spherical droplets in order to minimize the surface tension, the amphiphilic nature of charged solute molecules leads to the formation of supramolecular assemblies having cylindrical shape driven by charge repulsion between the ionic groups located on the surface of the aggregates. We show that formation of non-spherical micelles is the geometrical consequence if the fullerene derivatives are considered as surfactants where the ionized groups are only hydrophilic unit. The agglomeration behavior of fullerenes is evaluated by determining sizes of the clusters, solvent accessible surface areas, and shape parameters. By changing the size of the counterions from chloride over iodide to perchlorate we find a thickening of the cylinder-like structures which can be explained by stronger condensation of larger ions and thus partial screening of the charge repulsion on the cluster surface. The reason for the size dependence of counterion condensation is the formation of a stronger hydration shell in case of small ions which in turn are repelled from the fullerene aggregates. Simulations are also in good agreement with the experimentally observed morphologies of decorated C60-nanoparticles.