Penetration Barrier of Water through Graphynes’ Pores: First-Principles Predictions and Force Field Optimization

Abstract

Graphynes are novel two-dimensional carbon-based materials that have been proposed as molecular filters, especially for water purification technologies. We carry out first-principles electronic structure calculations at the MP2C level of theory to assess the interaction between water and graphyne, graphdiyne, and graphtriyne pores. The computed penetration barriers suggest that water transport is unfeasible through graphyne while being unimpeded for graphtriyne. For graphdiyne, with a pore size almost matching that of water, a low barrier is found that in turn disappears if an active hydrogen bond with an additional water molecule on the opposite side of the opening is considered. Thus, in contrast with previous determinations, our results do not exclude graphdiyne as a promising membrane for water filtration. In fact, present calculations lead to water permeation probabilities that are 2 orders of magnitude larger than estimations based on common force fields. A new pair potential for the water-carbon noncovalent component of the interaction is proposed for molecular dynamics simulations involving graphdiyne and water.

First principles investigation of hydrogen physical adsorption on graphynes' layers

“…1 we report the planar molecular structures that can be considered as the smallest precursors [10,20] 1) are kept frozen during the calculations and are those providing for each case both the deepest interaction well and the lowest repulsive well at short distances. In the case of graphene the minimum is located at about 2.9Å from the plane and the related well depth is about 53 meV.…”

“…The number n of acetylenic linkages which connect the benzene rings defines the different graphyne-n species and the first three members of the family are known as graphyne, graphdiyne and graphtriyne, respectively [7], and they feature nanopores of increasing size. The successful synthesis of graphynes has led to important theoretical studies devoted to their application as effective single-layer membranes for gas separation and water filtration technologies [8][9][10][11].…”

“…More accurate estimations for the noncovalent H 2 -graphynes interaction are therefore desirable and their calculations would require reliable computational approaches. Our choice is to use the "coupled" supermolecular second-order Møller-Plesset 4 perturbation theory (MP2C) which has been reported to provide reliable estimations for weakly bound systems such as rare gas-fullerene [19] and -coronene [20] as well as water(rare gas)-graphynes' pores [10,11].…”

Graphdiyne Filter for Decontaminating Lead‐Ion‐Polluted Water

“…[13,14] This material has attracted great attention due to its impressive properties, such as high carrier mobility, [15] high nonlinear optical susceptibility, [16] low thermal conductivity, [17] and uniformly distributed pores, which are defined by the atomic structure of graphdiyne. Graphdiyne has been proposed as a promising material for application in electronic devices, energy storage, [18] gas separation, [19,20] metal-free catalysis, [21] water purification, [22,23] etc. A number of studies have examined the synthesis of this material, and graphdiyne with different morphologies [24][25][26][27] and oligomeric subunits of graphdiyne [13,28] have been achieved.…”

Atomic cluster collisions: ISACC-2015 (7th International Symposium)*

“…1) on many different types of clusters and processes, e.g. weakly bound van der Waals (vdW), metallic [8][9][10], nanodroplets [11][12][13], fullerenes [14,15] PAHs (Polycyclic Aromatic Hydrocarbons)/carbon-layered [16][17][18][19], water and mixed-water clusters [20][21][22][23][24] and clathrates [25,26]; spectroscopic and collisional processes of excited molecules in the gas phase [27][28][29]; production of charged cluster ions [30]; electron impact ionization of clusters; Coulomb explosion [31,32]; high harmonic generation [33]; photon/electron irradiation [34]; photo-electron spectra of small clusters [35]; nanoplasma generated in atomic and molecular clusters by intense laser pulses [36]; phase diagrams including supercritical phases [37], and eventually, spectroscopy [38] and molecular dynamics studies involving biological media and medical applications [39][40][41][42].The contributions to this issue represent the studies both at the fundamental level of elementary mechanisms …”