In this paper, we study the interfacial friction of water at graphitic interfaces with various topologies, water between planar graphene sheets, inside and outside carbon nanotubes, with the goal to disentangle confinement and curvature effects on friction. We show that the friction coefficient exhibits a strong curvature dependence; while friction is independent of confinement for the graphene slab, it decreases with carbon nanotube radius for water inside, but increases for water outside. As a paradigm the friction coefficient is found to vanish below a threshold diameter for armchair nanotubes. Using a statistical description of the interfacial friction, we highlight here a structural origin of this curvature dependence, mainly associated with a curvature-induced incommensurability between the water and carbon structures. These results support the recent experiments reporting fast transport of water in nanometric carbon nanotube membranes.

Friction is one of the main sources of dissipation at liquid water/solid interfaces. Despite recent progress, a detailed understanding of water/solid friction in connection with the structure and energetics of the solid surface is lacking. Here we show for the first time that ab initio molecular dynamics can be used to unravel the connection between the structure of nanoscale water and friction for liquid water in contact with graphene and with hexagonal boron nitride. We find that whilst the interface presents a very similar structure between the two sheets, the friction coefficient on boron nitride is ≈ 3 times larger than that on graphene. This comes about because of the greater corrugation of the energy landscape on boron nitride arising from specific electronic structure effects. We discuss how a subtle dependence of the friction on the atomistic details of a surface, that is not related to its wetting properties, may have a significant impact on the transport of water at the nanoscale, with implications for the development of membranes for desalination and for osmotic power harvesting.Nanofluidics is an exciting field that offers alternative and sustainable solutions to problems relating to energy conversion, water filtration and desalination [1][2][3][4][5][6][7][8][9]. Miniaturization towards nanofluidic devices inevitably leads to an enhanced influence of surface and interface properties as opposed to those of the bulk. Friction is the most important interface property that limits fluid transport at the nanoscale, and its understanding is therefore crucial for the design of more efficient membranes, nanotubes and pores that exhibit low liquid/solid friction. The behavior of liquid flow at scales on the order of a few tens of nanometres departs from continuum fluid dynamics and desirable transport properties emerge at such small scales [10]. For instance, carbon nanotubes have a very high water permeability as compared to the prediction of macroscopic fluid dynamics [2]. Further, a vanishing friction has been found, giving rise to superlubric behavior of water chains inside tubes of sub-nanometre radii [11].Besides carbon, boron nitride (BN) nanostructures have recently been explored for the development of nanofluidic devices for fast water transport and efficient power generation [1,12,13]. Recent interest has been fueled by the demonstration that salinity concentration gradients across BN nanotube membranes can leed to the generation of very large electric currents [1]. It has also very recently been shown that there is a very large interlayer friction between in multiwalled BN nanotubes [14], as opposed to the superlubric behavior of the (homopolar) carbon nanotubes [15]. This suggests that the frictional properties of BN and C nanostructures might be quite different. However, to the best of our knowledge there has been no attempt to measure or compute the friction of water at the interface with BN sheets or nanotubes. Given that ab initio results have shown very similar contact angles of water drople...

We show, using extensive molecular dynamics simulations, that the dynamics of the electric double layer (EDL) is very much dependent on the wettability of the charged surface on which the EDL develops. For a wetting surface, the dynamics, characterized by the so-called zeta potential, is mainly controlled by the electric properties of the surface, and our work provides a clear interpretation for the traditionally introduced immobile Stern layer. In contrast, the immobile layer disappears for nonwetting surfaces, and the zeta potential deduced from electrokinetic effects is considerably amplified by the existence of a slippage at the solid substrate.

Hydrodynamic behavior at the vicinity of a confining wall is closely related to the friction properties of the liquid/solid interface. Here we consider, using Molecular Dynamics simulations, the electric contribution to friction for charged surfaces, and the induced modification of the hydrodynamic boundary condition at the confining boundary. The consequences of liquid slippage for electrokinetic phenomena, through the coupling between hydrodynamics and electrostatics within the electric double layer, are explored. Strong amplification of electro-osmotic effects is revealed, and the non-trivial effect of surface charge is discussed. This work allows to reconsider existing experimental data, concerning ζ potentials of hydrophobic surfaces and suggest the possibility to generate "giant" electro-osmotic and electrophoretic effects, with direct applications in microfluidics.

Ion transport through nanopores drilled in thin membranes is central to numerous applications, including biosensing and ion selective membranes. This paper reports experiments, numerical calculations, and theoretical predictions demonstrating an unexpectedly large ionic conduction in solid-state nanopores, taking its origin in anomalous entrance effects. In contrast to naive expectations based on analogies with electric circuits, the surface conductance inside the nanopore is shown to perturb the three-dimensional electric current streamlines far outside the nanopore in order to meet charge conservation at the pore entrance. This unexpected contribution to the ionic conductance can be interpreted in terms of an apparent electric size of the solid-state nanopore, which is much larger than its geometric counterpart whenever the number of charges carried by the nanopore surface exceeds its bulk counterpart. This apparent electric size, which can reach hundreds of nanometers, can have a major impact on the electrical detection of translocation events through nanopores, as well as for ionic transport in biological nanopores.

The ubiquitous aquaporin channels are able to conduct water across cell membranes, combining the seemingly antagonist functions of a very high selectivity with a remarkable permeability. Whereas molecular details are obvious keys to perform these tasks, the overall efficiency of transport in such nanopores is also strongly limited by viscous dissipation arising at the connection between the nanoconstriction and the nearby bulk reservoirs. In this contribution, we focus on these so-called entrance effects and specifically examine whether the characteristic hourglass shape of aquaporins may arise from a geometrical optimum for such hydrodynamic dissipation. Using a combination of finite-element calculations and analytical modeling, we show that conical entrances with suitable opening angle can indeed provide a large increase of the overall channel permeability. Moreover, the optimal opening angles that maximize the permeability are found to compare well with the angles measured in a large variety of aquaporins. This suggests that the hourglass shape of aquaporins could be the result of a natural selection process toward optimal hydrodynamic transport. Finally, in a biomimetic perspective, these results provide guidelines to design artificial nanopores with optimal performances. nanofluidics | hydrodynamic permeability | biochannels

In this contribution, we study situations in which nanoparticles in a fluid are strongly heated, generating high heat fluxes. This situation is relevant to experiments in which a fluid is locally heated by using selective absorption of radiation by solid particles. We first study this situation for different types of molecular interactions, using models for gold particles suspended in octane and in water. As already reported in experiments, very high heat fluxes and temperature elevations (leading eventually to particle destruction) can be observed in such situations. We show that a very simple modeling based on Lennard-Jones (LJ) interactions captures the essential features of such experiments and that the results for various liquids can be mapped onto the LJ case, provided a physically justified (corresponding state) choice of parameters is made. Physically, the possibility of sustaining very high heat fluxes is related to the strong curvature of the interface that inhibits the formation of an insulating vapor film.interfaces ͉ liquids ͉ Kapitsa resistance S ubmicron-scale heat transfer is attracting a growing interest, motivated by both fundamental and technological points of view. In fluids, considerable attention has been devoted to the so-called nanofluids (1, 2), in which nanoparticles in dilute suspension appear to modify both bulk heat transfer and critical heat fluxes. Although the former effect can presumably be understood in terms of particle aggregation (3, 4), the latter is still poorly understood.More generally, heat transfer from nanoparticles or nanostructures to a fluid environment is a subject of active research, stimulated by the development of experimental techniques such as time-resolved optical absorption or reflectivity or photothermal correlation spectroscopy (5). Applications include, e.g., the enhancement of cooling from structured surfaces, local heating of fluids by selective absorption from nanoparticles, with possible biomedical hyperthermia uses (6, 7). Recent experiments demonstrated the possibility of reaching very high local temperatures by using laser heating of nanoparticles (8-10), even reaching the melting point of gold particles suspended in water. From a conceptual point of view, such experiments raise many interesting questions compared with usual, macroscopic heattransfer experiments. How are the phase diagram and heattransfer equations modified at small scales? How relevant is the presence of interfacial resistances, and how do they change with temperature?The case of nanofluids (11) is a good illustration of the role that can be played by molecular simulation in the interpretation of such complex situations. Although many interpretations have been proposed to explain the reported experimental results, it is only simulation of simple models that has been able to disprove some of these interpretations and to demonstrate the validity of the alternative, aggregation scenario. Interestingly, the use of complex models with accurate interaction force fields is not, in genera...

In this work, we perform a theoretical study of liquid flow in graphitic nanopores of different sizes and geometries. Molecular dynamics flow simulations of different liquids (water, decane, ethanol, and OMCTS) in carbon nanotubes (CNT) are shown to exhibit flow velocities 1-3 orders of magnitude higher than those predicted from the continuum hydrodynamics framework and the no-slip boundary condition. These results support previous experimental findings obtained by several groups that reported exceptionally high liquid flow rates in CNT membranes. The liquid/graphite friction coefficient is identified as the crucial parameter for this fast mass transport in CNT. The friction coefficient is found to be very sensitive to wall curvature: friction is independent of confinement for liquids between flat graphene walls with zero curvature, whereas it decreases with increasing positive curvature (liquid inside CNT), and it increases with increasing negative curvature (liquid outside CNT). Furthermore, we present a theoretical approximate expression for the friction coefficient, which predicts qualitatively and semiquantitatively its curvature dependent behavior. The proposed theoretical description, which works well for different kinds of liquids (alcohols, alkanes, and water), sheds light on the physical mechanisms at the origin of the ultra low liquid/solid friction in CNT. In fact, it is due to their perfectly ordered molecular structure and their atomically smooth surface that carbon nanotubes are quasiperfect liquid conductors compared to other membrane pores like nanochannels in amorphous silica.