Ultra-thin proton conducting carrier layers for scalable integration of atomically thin 2D materials with proton exchange polymers for next-generation PEMs.

Scalable approaches for synthesis and integration of proton selective atomically thin 2D materials with proton conducting polymers can enable next-generation proton exchange membranes (PEMs) with minimal crossover of reactants or undesired species while maintaining adequately high proton conductance for practical applications. Here, we systematically investigate facile and scalable approaches to interface monolayer graphene synthesized via scalable chemical vapor deposition (CVD) on Cu foil with the most widely used proton exchange polymer Nafion 211 (N211, ∼25 µm thick film) via (i) spin-coating a ∼700 nm thin Nafion carrier layer to transfer graphene (spin + scoop), (ii) casting a Nafion film and cold pressing (cold press), and (iii) hot pressing (hot press) while minimizing micron-scale defects to <0.3% area. Interfacing CVD graphene on Cu with N211 via cold press or hot press and subsequent removal of Cu via etching results in ∼50% lower areal proton conductance compared to membranes fabricated via the spin + scoop method. Notably, the areal proton conductance can be recovered by soaking the hot and cold press membranes in 0.1 M HCl, without significant damage to graphene. We rationalize our finding by the significantly smaller reservoir for cation uptake from Cu etching for the ∼700 nm thin carrier Nafion layer used for spin + scoop transfer compared to the ∼25 µm thick N211 film for hot and cold pressing. Finally, we demonstrate performance in H2 fuel cells with power densities of ∼0.23 W cm-2 and up to ∼41-54% reduction in H2 crossover for the N211|G|N211 sandwich membranes compared to the control N211|N211 indicating potential for our approach in enabling advanced PEMs for fuel cells, redox-flow batteries, isotope separations and beyond.

A Review of Scalable Hexagonal Boron Nitride (h-BN) Synthesis for Present and Future Applications.

Hexagonal boron nitride (h-BN) is a layered inorganic synthetic crystal exhibiting high temperature stability and high thermal conductivity. As a ceramic material it has been widely used for thermal management, heat shielding, lubrication, and as a filler material for structural composites. Recent scientific advances in isolating atomically thin monolayers from layered van der Waals crystals to study their unique properties has propelled research interest in mono/few layered h-BN as a wide bandgap insulating support for nanoscale electronics, tunnel barriers, communications, neutron detectors, optics, sensing, novel separations, quantum emission from defects, among others. Realizing these futuristic applications hinges on scalable cost-effective high-quality h-BN synthesis. Here, the authors review scalable approaches of high-quality mono/multilayer h-BN synthesis, discuss the challenges and opportunities for each method, and contextualize their relevance to emerging applications. Maintaining a stoichiometric balance B:N = 1 as the atoms incorporate into the growing layered crystal and maintaining stacking order between layers during multi-layer synthesis emerge as some of the main challenges for h-BN synthesis and the development of processes to address these aspects can inform and guide the synthesis of other layered materials with more than one constituent element. Finally, the authors contextualize h-BN synthesis efforts along with quality requirements for emerging applications via a technological roadmap.

Nanoporous Atomically Thin Graphene Filters for Nanoscale Aerosols.

Filtering nanoparticulate aerosols from air streams is important for a wide range of personal protection equipment (PPE), including masks used for medical research, healthcare, law enforcement, first responders, and military applications. Conventional PPEs capable of filtering nanoparticles <300 nm are typically bulky and sacrifice breathability to maximize protection from exposure to harmful nanoparticulate aerosols including viruses ∼20-300 nm from air streams. Here, we show that nanopores introduced into centimeter-scale monolayer graphene supported on polycarbonate track-etched supports via a facile oxygen plasma etch can allow for filtration of aerosolized SiO2 nanoparticles of ∼5-20 nm from air steams while maintaining air permeance of ∼2.28-7.1 × 10-5 mol m-2 s-1 Pa-1. Furthermore, a systematic increase in oxygen plasma etch time allows for a tunable size-selective filtration of aerosolized nanoparticles. We demonstrate a new route to realize ultra-compact, lightweight, and conformal form-factor filters capable of blocking sub-20 nm aerosolized nanoparticles with particular relevance for biological/viral threat mitigation.

Visualizing Oxidation Mechanisms in Few-Layered Black Phosphorus via In Situ Transmission Electron Microscopy.

Layered two-dimensional (2D) black phosphorus (BP) exhibits novel semiconducting properties including a tunable bandgap and high electron mobility. However, the poor stability of BP in ambient environment severely limits potential for application in future electronic and optoelectronic devices. While passivation or encapsulation of BP using inert materials/polymers has emerged as a plausible solution, a detailed fundamental understanding of BP's reaction with oxygen is imperative to rationally advance its use in applications. Here, we use in situ environmental transmission electron microscopy to elucidate atomistic structural changes in mechanically exfoliated few-layered BP during exposure to varying partial pressures of oxygen. An amorphous oxide layer is seen on the actively etching BP edges, and the thickness of this layer increases with increasing oxygen partial pressure, indicating that oxidation proceeds via initial formation of amorphous PxOy species which sublime to result in the etching of the BP crystal. We observe that while few-layered BP is stable under the 80 kV electron beam (e-beam) in vacuum, the lattice oxidizes and degrades at room temperature in the presence of oxygen only in the region under the e-beam. The oxidative etch rate also increases with increasing e-beam dosage, suggesting the presence of an energy barrier for the oxidation reaction. Preferential oxidative etching along the [0 0 1] and [0 0 1] crystallographic directions is observed, in good agreement with density functional theory calculations showing favorable thermodynamic stability of the oxidized BP (0 0 1) planes compared to the (1 0 0) planes. We expect the atomistic insights and fundamental understanding obtained here to aid in the development of novel approaches to integrate BP in future applications.