title: Three-Dimensional Graphene-Based Microbarriers for Controlling Release and Reactivity in Colloidal Liquid Phases.
abstract: Two-dimensional materials are of great interest as high-performance molecular barriers. Graphene in particular is atomically thin, is impermeable to all molecules, and in some forms can be easily deposited over large areas into planar multilayer films that have been shown to suppress molecular transport. Graphene and graphene oxide sheets are also known to spontaneously self-assemble at liquid-liquid interfaces on the surfaces of dispersed droplets, but much less is known about the barrier properties of these ultrathin films in 3D curved microgeometries. This article demonstrates that 3D films self-assembled from graphene oxide or reduced graphene oxide sheets can be exploited to control the release of small molecules from dispersed liquid phase droplets by evaporation. The release rate and containment time can be tuned by addition of multivalent cations that recruit additional sheets from the bulk liquid to the interface, which is shown by molecular dynamics to occur by an electrostatic bridging mechanism. 3D graphene-based films on droplet surfaces can also be used to control the release and transport of soluble molecules from the droplet to surrounding bulk solvent phases. In some cases, the release can be effectively stopped to produce unique kinetically trapped emulsion phases consisting of two fully miscible but segregated liquids. Finally, interfacial graphene-based films are also shown to control interfacial chemical reaction processes by serving as transport barriers between the phases or by intercepting reactive cross-phase molecular collisions. This reaction control is demonstrated by using 3D graphene-based microbarriers to protect oxidation-sensitive oils from attack by aqueous-phase reactive oxygen species, which is an undesirable pathway implicated in many chemical product degradation and spoilage processes.
authors.affiliation: School of Engineering, Brown University , 182 Hope Street, Providence, Rhode Island 02912, United States.
authors.forename: Megan A
authors.initials: MA
authors.lastname: Creighton
authors.affiliation: School of Engineering, Brown University , 182 Hope Street, Providence, Rhode Island 02912, United States.
authors.forename: Wenpeng
authors.initials: W
authors.lastname: Zhu
authors.affiliation: School of Engineering, Brown University , 182 Hope Street, Providence, Rhode Island 02912, United States.
authors.forename: Finn
authors.initials: F
authors.lastname: van Krieken
authors.affiliation: School of Engineering, Brown University , 182 Hope Street, Providence, Rhode Island 02912, United States.
authors.forename: Robert A
authors.initials: RA
authors.lastname: Petteruti
authors.affiliation: School of Engineering, Brown University , 182 Hope Street, Providence, Rhode Island 02912, United States.
authors.forename: Huajian
authors.initials: H
authors.lastname: Gao
authors.affiliation: School of Engineering, Brown University , 182 Hope Street, Providence, Rhode Island 02912, United States.
authors.forename: Robert H
authors.initials: RH
authors.lastname: Hurt
keywords: Pickering emulsion; barrier technologies; controlled release; graphene oxide; molecular dynamics; self assembly