Deconstructing proton transport through atomically thin monolayer CVD graphene membranes

Chaturvedi, Pavan; Moehring, Nicole K.; Cheng, Peifu; Vlassiouk, Ivan; Boutilier, Michael S. H.; Kidambi, Piran R.

doi:10.1039/d2ta01737g

Title: Deconstructing proton transport through atomically thin monolayer CVD graphene membranes

Journal Article · Wed Apr 20 00:00:00 EDT 2022 · Journal of Materials Chemistry. A

DOI:https://doi.org/10.1039/d2ta01737g· OSTI ID:1883851

^[1]; Moehring, Nicole K. ^[1];

^[1];

^[2]; Boutilier, Michael S. H. ^[3];

^[1]

Vanderbilt University, Nashville, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Western University, London (Canada)

Selective proton (H⁺) permeation through the atomically thin lattice of graphene and other 2D materials offers new opportunities for energy conversion/storage and novel separations. Practical applications necessitate scalable synthesis via approaches such as chemical vapor deposition (CVD) that inevitably introduce sub-nanometer defects, grain boundaries and wrinkles, and understanding their influence on H⁺ transport and selectivity for large-area membranes is imperative but remains elusive. Using electrically driven transport of H⁺ and potassium ions (K⁺) we probe the influence of intrinsic sub-nanometer defects in monolayer CVD graphene across length-scales for the first time. At the micron scale, the areal H⁺ conductance of CVD graphene (~4.5-6 mS cm^-2) is comparable to that of mechanically exfoliated graphene indicating similarly high crystalline quality within a domain, albeit with K⁺ transport (~1.7 mS cm^-2). However, centimeter-scale Nafion|graphene|Nafion devices with several graphene domains show areal H⁺ conductance of ~339 mS cm^-2 and K⁺ conductance of ~23.8 mS cm^-2 (graphene conductance for H⁺ is ~1735 mS cm^-2 and for K⁺ it is ~47.6 mS cm^-2). Using a mathematical-transport-model and Nafion filled polycarbonate track etched supports, we systematically deconstruct the observed orders of magnitude increase in H⁺ conductance for centimeter-scale CVD graphene. The mitigation of defects (>1.6 nm), wrinkles and tears via interfacial polymerization results in a conductance of ~1848 mS cm^-2 for H⁺ and ~75.3 mS cm^-2 for K⁺ (H⁺/K⁺ selectivity of ~24.5) via intrinsic sub-nanometer proton selective defects in CVD graphene. We demonstrate atomically thin membranes with significantly higher ionic selectivity than state-of-the-art proton exchange membranes while maintaining comparable H⁺ conductance. Our work provides a new framework to assess H⁺ conductance and selectivity of large-area 2D membranes and highlights the role of intrinsic sub-nanometer proton selective defects for practical applications.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Vanderbilt Univ., Nashville, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC); National Science Foundation (NSF); ECS-Toyota Young Investigator Fellowship; Vanderbilt University

Grant/Contract Number:: AC05-00OR22725; NSF-1944134; SC0022237

OSTI ID:: 1883851

Alternate ID(s):: OSTI ID: 1868127; OSTI ID: 2324829

Journal Information:: Journal of Materials Chemistry. A, Vol. 10, Issue 37; ISSN 2050-7488

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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