Kinetic Control of Angstrom-Scale Porosity in 2D Lattices for Direct Scalable Synthesis of Atomically Thin Proton Exchange Membranes

Nicole K. Moehring; Pavan Chaturvedi; Peifu Cheng; Wonhee Ko; An Ping Li; Michael S.H. Boutilier; Piran R. Kidambi

doi:10.1021/acsnano.2c03730

Kinetic Control of Angstrom-Scale Porosity in 2D Lattices for Direct Scalable Synthesis of Atomically Thin Proton Exchange Membranes

Nicole K. Moehring, Pavan Chaturvedi, Peifu Cheng, Wonhee Ko, An Ping Li, Michael S.H. Boutilier, Piran R. Kidambi

Scanning Tunneling Microscopy Group

Research output: Contribution to journal › Article › peer-review

8 Scopus citations

Abstract

Angstrom-scale pores introduced into atomically thin 2D materials offer transformative advances for proton exchange membranes in several energy applications. Here, we show that facile kinetic control of scalable chemical vapor deposition (CVD) can allow for direct formation of angstrom-scale proton-selective pores in monolayer graphene with significant hindrance to even small, hydrated ions (K⁺diameter ∼6.6 Å) and gas molecules (H₂kinetic diameter ∼2.9 Å). We demonstrate centimeter-scale Nafion|Graphene|Nafion membranes with proton conductance ∼3.3-3.8 S cm^-2(graphene ∼12.7-24.6 S cm^-2) and H⁺/K⁺selectivity ∼6.2-44.2 with liquid electrolytes. The same membranes show proton conductance ∼4.6-4.8 S cm^-2(graphene ∼39.9-57.5 S cm^-2) and extremely low H₂crossover ∼1.7 × 10^-1- 2.2 × 10^-1mA cm^-2(∼0.4 V, ∼25 °C) with H₂gas feed. We rationalize our findings via a resistance-based transport model and introduce a stacking approach that leverages combinatorial effects of interdefect distance and interlayer transport to allow for Nafion|Graphene|Graphene|Nafion membranes with H⁺/K⁺selectivity ∼86.1 (at 1 M) and record low H₂crossover current density ∼2.5 × 10^-2mA cm^-2, up to ∼90% lower than state-of-the-art ionomer Nafion membranes ∼2.7 × 10^-1mA cm^-2under identical conditions, while still maintaining proton conductance ∼4.2 S cm^-2(graphene stack ∼20.8 S cm^-2) comparable to that for Nafion of ∼5.2 S cm^-2. Our experimental insights enable functional atomically thin high flux proton exchange membranes with minimal crossover.

Original language	English
Pages (from-to)	16003-16018
Number of pages	16
Journal	ACS Nano
Volume	16
Issue number	10
DOIs	https://doi.org/10.1021/acsnano.2c03730
State	Published - Oct 25 2022

Funding

This research was supported in part by the U.S. Department of Energy Isotope Program, managed by the Office of Science for Isotope R&D and Production under award number DE-SC0022237, in part by faculty start-up funds from Vanderbilt University to P.R.K, and in part by NSF CAREER award #1944134. P.R.K. acknowledges the ECS Toyota Young Investigator Fellowship. The STM imaging was performed at the Center for Nanophase Materials Sciences at Oak Ridge National Laboratory, a U.S. Department of Energy Office of Science User Facility. The use of Vanderbilt Institute of Nanoscale Science and Engineering CORE facilities are acknowledged. N.K.M and P.R.K. would like to thank and acknowledge helpful scientific discussions and insights from Prof. Peter Pintauro and Dr. Krysta Waldrop.

Funders	Funder number
Office of Science for Isotope R&D and Production	DE-SC0022237
National Science Foundation	1944134
U.S. Department of Energy
Vanderbilt University

Keywords

Angstrom-scale pores
atomically thin membranes
graphene membranes
hydrogen crossover
proton exchange membranes
proton selectivity

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1021/acsnano.2c03730

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title = "Kinetic Control of Angstrom-Scale Porosity in 2D Lattices for Direct Scalable Synthesis of Atomically Thin Proton Exchange Membranes",

abstract = "Angstrom-scale pores introduced into atomically thin 2D materials offer transformative advances for proton exchange membranes in several energy applications. Here, we show that facile kinetic control of scalable chemical vapor deposition (CVD) can allow for direct formation of angstrom-scale proton-selective pores in monolayer graphene with significant hindrance to even small, hydrated ions (K+diameter ∼6.6 {\AA}) and gas molecules (H2kinetic diameter ∼2.9 {\AA}). We demonstrate centimeter-scale Nafion|Graphene|Nafion membranes with proton conductance ∼3.3-3.8 S cm-2(graphene ∼12.7-24.6 S cm-2) and H+/K+selectivity ∼6.2-44.2 with liquid electrolytes. The same membranes show proton conductance ∼4.6-4.8 S cm-2(graphene ∼39.9-57.5 S cm-2) and extremely low H2crossover ∼1.7 × 10-1- 2.2 × 10-1mA cm-2(∼0.4 V, ∼25 °C) with H2gas feed. We rationalize our findings via a resistance-based transport model and introduce a stacking approach that leverages combinatorial effects of interdefect distance and interlayer transport to allow for Nafion|Graphene|Graphene|Nafion membranes with H+/K+selectivity ∼86.1 (at 1 M) and record low H2crossover current density ∼2.5 × 10-2mA cm-2, up to ∼90% lower than state-of-the-art ionomer Nafion membranes ∼2.7 × 10-1mA cm-2under identical conditions, while still maintaining proton conductance ∼4.2 S cm-2(graphene stack ∼20.8 S cm-2) comparable to that for Nafion of ∼5.2 S cm-2. Our experimental insights enable functional atomically thin high flux proton exchange membranes with minimal crossover.",

keywords = "Angstrom-scale pores, atomically thin membranes, graphene membranes, hydrogen crossover, proton exchange membranes, proton selectivity",

author = "Moehring, {Nicole K.} and Pavan Chaturvedi and Peifu Cheng and Wonhee Ko and Li, {An Ping} and Boutilier, {Michael S.H.} and Kidambi, {Piran R.}",

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doi = "10.1021/acsnano.2c03730",

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T1 - Kinetic Control of Angstrom-Scale Porosity in 2D Lattices for Direct Scalable Synthesis of Atomically Thin Proton Exchange Membranes

AU - Moehring, Nicole K.

AU - Chaturvedi, Pavan

AU - Cheng, Peifu

AU - Ko, Wonhee

AU - Li, An Ping

AU - Boutilier, Michael S.H.

AU - Kidambi, Piran R.

PY - 2022/10/25

Y1 - 2022/10/25

N2 - Angstrom-scale pores introduced into atomically thin 2D materials offer transformative advances for proton exchange membranes in several energy applications. Here, we show that facile kinetic control of scalable chemical vapor deposition (CVD) can allow for direct formation of angstrom-scale proton-selective pores in monolayer graphene with significant hindrance to even small, hydrated ions (K+diameter ∼6.6 Å) and gas molecules (H2kinetic diameter ∼2.9 Å). We demonstrate centimeter-scale Nafion|Graphene|Nafion membranes with proton conductance ∼3.3-3.8 S cm-2(graphene ∼12.7-24.6 S cm-2) and H+/K+selectivity ∼6.2-44.2 with liquid electrolytes. The same membranes show proton conductance ∼4.6-4.8 S cm-2(graphene ∼39.9-57.5 S cm-2) and extremely low H2crossover ∼1.7 × 10-1- 2.2 × 10-1mA cm-2(∼0.4 V, ∼25 °C) with H2gas feed. We rationalize our findings via a resistance-based transport model and introduce a stacking approach that leverages combinatorial effects of interdefect distance and interlayer transport to allow for Nafion|Graphene|Graphene|Nafion membranes with H+/K+selectivity ∼86.1 (at 1 M) and record low H2crossover current density ∼2.5 × 10-2mA cm-2, up to ∼90% lower than state-of-the-art ionomer Nafion membranes ∼2.7 × 10-1mA cm-2under identical conditions, while still maintaining proton conductance ∼4.2 S cm-2(graphene stack ∼20.8 S cm-2) comparable to that for Nafion of ∼5.2 S cm-2. Our experimental insights enable functional atomically thin high flux proton exchange membranes with minimal crossover.

AB - Angstrom-scale pores introduced into atomically thin 2D materials offer transformative advances for proton exchange membranes in several energy applications. Here, we show that facile kinetic control of scalable chemical vapor deposition (CVD) can allow for direct formation of angstrom-scale proton-selective pores in monolayer graphene with significant hindrance to even small, hydrated ions (K+diameter ∼6.6 Å) and gas molecules (H2kinetic diameter ∼2.9 Å). We demonstrate centimeter-scale Nafion|Graphene|Nafion membranes with proton conductance ∼3.3-3.8 S cm-2(graphene ∼12.7-24.6 S cm-2) and H+/K+selectivity ∼6.2-44.2 with liquid electrolytes. The same membranes show proton conductance ∼4.6-4.8 S cm-2(graphene ∼39.9-57.5 S cm-2) and extremely low H2crossover ∼1.7 × 10-1- 2.2 × 10-1mA cm-2(∼0.4 V, ∼25 °C) with H2gas feed. We rationalize our findings via a resistance-based transport model and introduce a stacking approach that leverages combinatorial effects of interdefect distance and interlayer transport to allow for Nafion|Graphene|Graphene|Nafion membranes with H+/K+selectivity ∼86.1 (at 1 M) and record low H2crossover current density ∼2.5 × 10-2mA cm-2, up to ∼90% lower than state-of-the-art ionomer Nafion membranes ∼2.7 × 10-1mA cm-2under identical conditions, while still maintaining proton conductance ∼4.2 S cm-2(graphene stack ∼20.8 S cm-2) comparable to that for Nafion of ∼5.2 S cm-2. Our experimental insights enable functional atomically thin high flux proton exchange membranes with minimal crossover.

KW - Angstrom-scale pores

KW - atomically thin membranes

KW - graphene membranes

KW - hydrogen crossover

KW - proton exchange membranes

KW - proton selectivity

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Kinetic Control of Angstrom-Scale Porosity in 2D Lattices for Direct Scalable Synthesis of Atomically Thin Proton Exchange Membranes

Abstract

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Keywords

UN SDGs

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