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The emergence of new nanoporous materials, based e.g. on 2D materials, offers new avenues for water filtration and energy. There is accordingly a need to investigate the molecular mechanisms at the root of the advanced performances of these systems in terms of nanofluidic and ionic transport. In this work, we introduce a novel unified methodology for Non-Equilibrium classical Molecular Dynamic simulations (NEMD), allowing to apply likewise pressure, chemical potential and voltage drops across nanoporous membranes and quantifying the resulting observables characterizing confined liquid transport under such external stimuli. We apply the NEMD methodology to study a new type of synthetic Carbon NanoMembranes (CNM), which have recently shown outstanding performances for desalination, keeping high water permeability while maintaining full salt rejection. The high water permeance of CNM, as measured experimentally, is shown to originate in prominent entrance effects associated with negligible friction inside the nanopore. Beyond, our methodology allows to fully calculate the symmetric transport matrix and the cross-phenomena such as electro-osmosis, diffusio-osmosis, streaming currents, etc. In particular, we predict a large diffusio-osmotic current across the CNM pore under concentration gradient, despite the absence of surface charges. This suggests that CNMs are outstanding candidates as alternative, scalable membranes for osmotic energy harvesting., Comment: 13 pages, 16 figures, submitted to J. Chem Phys

We compute ionic free energy adsorption profiles at aqueous graphene interface by developing a self-consistent approach. To do so, we design a microscopic model for water and put the liquid on an equal footing with the graphene described by its electronic band structure. By evaluating progressively the electronic/dipolar coupled electrostatic interactions, we show that the coupling level including mutual graphene/water screening permits to recover remarkably the precision of extensive quantum simulations. We further derive the potential of mean force evolution of several alkali cations.

The possibility to control electrokinetic transport through carbon and hexagonal boron nitride (hBN) nanotubes has recently opened new avenues for nanofluidic approaches to face outstanding challenges such as energy production and conversion or water desalination. The $p$H-dependence of experimental transport coefficients point to the sorption of hydroxide ions as the microscopic origin of the surface charge and recent ab initio calculations suggest that these ions behave differently on carbon and hBN, with only physisorption on the former and both physi- and chemisorption on the latter. Using classical non-equilibrium molecular dynamics simulations of interfaces between an aqueous electrolyte and three models of hBN and graphite surfaces, we demonstrate the major influence of the sorption mode of hydroxide ions on the interfacial transport properties. Physisorbed surface charge leads to a considerable enhancement of the surface conductivity as compared to its chemisorbed counterpart, while values of the $\zeta$-potential are less affected . The analysis of the MD results for the surface conductivity and $\zeta$-potential in the framework of Poisson-Boltzmann-Stokes theory, as is usually done to analyze experimental data, further confirms the importance of taking into account both the mobility of surface hydroxide ions and the decrease of the slip length with increasing titratable surface charge density.

The flow of water in carbon nanochannels has defied understanding thus far, with accumulating experimental evidence for ultra-low friction, exceptionally high water flow rates, and curvature-dependent hydrodynamic slippage. These unique properties have raised considerable interest in carbon-based membranes for desalination, molecular sieving and energy harvesting. However, the mechanism of water-carbon friction remains unknown, with neither current theories, nor classical or ab initio molecular dynamics simulations providing satisfactory rationalisation for its singular behaviour. Here, we develop a quantum theory of the solid-liquid interface, which reveals a new contribution to friction, due to the coupling of charge fluctuations in the liquid to electronic excitations in the solid. We expect that this quantum friction, which is absent in Born-Oppenheimer molecular dynamics, is the dominant friction mechanism for water on carbon-based materials. As a key result, we demonstrate a dramatic difference in quantum friction between the water-graphene and water-graphite interface, due to the coupling of water Debye collective modes with a thermally excited plasmon specific to graphite. This suggests an explanation for the radius-dependent slippage of water in carbon nanotubes, in terms of the nanotubes' electronic excitations. Our findings open the way to quantum engineering of hydrodynamic flows through the confining wall electronic properties.

Graphene oxide is a rising star among 2D materials, yet its interaction with liquid water remains a fundamentally open question: experimental characterization at the atomic scale is difficult, and modelling by classical approaches cannot properly describe chemical reactivity. Here, we bridge the gap between simple computational models and complex experimental systems, by realistic first-principles molecular simulations of graphene oxide (GO) in liquid water. We construct chemically accurate GO models and study their behavior in water, showing that oxygen-bearing functional groups (hydroxyl and epoxides) are preferentially clustered on the graphene oxide layer. We demonstrated the specific properties of GO in water, an unusual combination of both hydrophilicity and fast water dynamics. Finally, we evidence that GO is chemically active in water, acquiring an average negative charge of the order of 10~mC m$^{-2}$. The ab initio modelling highlights the uniqueness of GO structures for applications as innovative membranes for desalination and water purification.

Aqueous proton transport at interfaces is ubiquitous and crucial for a number of fields, ranging from cellular transport and signaling, to catalysis and membrane science. However, due to their light mass, small size and high chemical reactivity, uncovering single proton surface transport at room temperature and in aqueous environment has so far remained out-of-reach of conventional atomic-scale surface science techniques, such as STM. Here, we use single-molecule localization microscopy techniques to resolve optically the transport of individual excess protons at the interface of hexagonal boron nitride crystals and aqueous solutions at room temperature. Our label-free approach relies on the successive protonation and activation of optically active defects at the surface of the crystal allowing us to resolve interfacial proton transport at the single molecule scale with nanometric resolution and over micrometer range. Proton trajectories are revealed as a succession of jumps between proton-binding defects, mediated by interfacial water. We demonstrate unexpected interfacial proton mobility under illumination, limited by proton desorption from individual defects. The proposed mechanism is supported by ab initio molecular dynamics simulations of defected and pristine hBN/water interface. Our observations provide direct experimental evidence at the single molecule scale that interfacial water provides a preferential pathway for lateral proton transport. Our findings have fundamental and general implications for water-mediated molecular charge transport at interfaces.

The electronic structure of a single layer graphene on Ru(0001) is compared with that of a single layer hexagonal boron nitride nanomesh on Ru(0001). Both are corrugated sp2 networks and display a pi-band gap at the K point of their 1 x 1 Brillouin zone. Graphene has a distinct Fermi surface which indicates that 0.1 electrons are transferred per 1 x 1 unit cell. Photoemission from adsorbed xenon identifies two distinct Xe 5p1/2 lines, separated by 240 meV, which reveals a corrugated electrostatic potential energy surface. These two Xe species are related to the topography of the system and have different desorption energies., Comment: 5 pages, 4 figures, 1 table