Online citations, reference lists, and bibliographies.
← Back to Search

Proton Transport Through One-atom-thick Crystals

S. Hu, M. Lozada-Hidalgo, F. Wang, A. Mishchenko, F. Schedin, R. Nair, E. Hill, D. Boukhvalov, M. Katsnelson, R. Dryfe, I. Grigorieva, H. A. Wu, Andre K. Geim
Published 2014 · Chemistry, Physics, Medicine

Save to my Library
Download PDF
Analyze on Scholarcy Visualize in Litmaps
Share
Reduce the time it takes to create your bibliography by a factor of 10 by using the world’s favourite reference manager
Time to take this seriously.
Get Citationsy
Graphene is increasingly explored as a possible platform for developing novel separation technologies. This interest has arisen because it is a maximally thin membrane that, once perforated with atomic accuracy, may allow ultrafast and highly selective sieving of gases, liquids, dissolved ions and other species of interest. However, a perfect graphene monolayer is impermeable to all atoms and molecules under ambient conditions: even hydrogen, the smallest of atoms, is expected to take billions of years to penetrate graphene’s dense electronic cloud. Only accelerated atoms possess the kinetic energy required to do this. The same behaviour might reasonably be expected in the case of other atomically thin crystals. Here we report transport and mass spectroscopy measurements which establish that monolayers of graphene and hexagonal boron nitride (hBN) are highly permeable to thermal protons under ambient conditions, whereas no proton transport is detected for thicker crystals such as monolayer molybdenum disulphide, bilayer graphene or multilayer hBN. Protons present an intermediate case between electrons (which can tunnel easily through atomically thin barriers) and atoms, yet our measured transport rates are unexpectedly high and raise fundamental questions about the details of the transport process. We see the highest room-temperature proton conductivity with monolayer hBN, for which we measure a resistivity to proton flow of about 10 Ω cm2 and a low activation energy of about 0.3 electronvolts. At higher temperatures, hBN is outperformed by graphene, the resistivity of which is estimated to fall below 10−3 Ω cm2 above 250 degrees Celsius. Proton transport can be further enhanced by decorating the graphene and hBN membranes with catalytic metal nanoparticles. The high, selective proton conductivity and stability make one-atom-thick crystals promising candidates for use in many hydrogen-based technologies.
This paper references
10.1063/1.1744059
Electrochemical Behavior of the Palladium‐Hydrogen System. I. Potential‐Determining Mechanisms
S. Schuldiner (1958)
10.1088/0022-3735/19/1/016
A proton-injecting technique for the measurement of hydration-dependent protonic conductivity
H. Morgan (1986)
10.1021/CM00030A009
A new route to metal hydrides
D. Murphy (1993)
10.1103/PhysRevB.54.1703
Separable dual-space Gaussian pseudopotentials.
Goedecker (1996)
10.1149/1.1836625
Proton Conductivity of Nafion 117 as Measured by a Four‐Electrode AC Impedance Method
Yoshitsugu Sone (1996)
10.1063/1.1329672
A climbing image nudged elastic band method for finding saddle points and minimum energy paths
G. Henkelman (2000)
10.1016/S0376-7388(00)00635-9
Polymeric proton conducting membranes for medium temperature fuel cells (110–160°C)
G. Alberti (2001)
10.1016/S0370-1573(02)00633-6
Quantum properties of atomic-sized conductors
N. Agrait (2003)
10.1016/J.ELECTACTA.2004.02.035
Solution-cast Nafion® ionomer membranes: preparation and characterization
R. F. Silva (2004)
10.1021/CR0207123
State of understanding of nafion.
K. A. Mauritz (2004)
10.1073/pnas.0502848102
Two-dimensional atomic crystals.
K. Novoselov (2005)
10.1016/j.cpc.2004.12.014
Quickstep: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach
J. VandeVondele (2005)
10.1016/J.MEMSCI.2006.05.025
Nafion®/poly(vinyl alcohol) blends: Effect of composition and annealing temperature on transport properties
Nicholas W. DeLuca (2006)
10.1063/1.2770708
Gaussian basis sets for accurate calculations on molecular systems in gas and condensed phases.
J. VandeVondele (2007)
10.1021/ja804409f
Selective ion passage through functionalized graphene nanopores.
Kyaw Sint (2008)
10.1021/nl0808684
Graphene oxidation: thickness-dependent etching and strong chemical doping.
L. Liu (2008)
10.1021/nl801457b
Impermeable atomic membranes from graphene sheets.
J. Bunch (2008)
10.1063/1.3021413
Graphene: A perfect nanoballoon
O. Leenaerts (2008)
10.1021/jp9036777
Proton transfer and proton concentrations in protonated Nafion fuel cell membranes.
D. Spry (2009)
10.1021/nl9021946
Porous graphene as the ultimate membrane for gas separation.
De-En Jiang (2009)
10.1021/nl803087x
Observation of graphene bubbles and effective mass transport under graphene films.
E. Stolyarova (2009)
Porous graphene as the ultimatemembrane for gas separation
D. E. Jiang (2009)
10.1088/1367-2630/12/12/125012
Graphene hydrate: theoretical prediction of a new insulating form of graphene
W. Wang (2010)
10.1021/nl101399r
On resonant scatterers as a factor limiting carrier mobility in graphene.
Z. Ni (2010)
10.1038/nature09379
Graphene as a sub-nanometer trans-electrode membrane
S. Garaj (2010)
10.1063/1.3492845
Graphene as a transparent conductive support for studying biological molecules by transmission electron microscopy
R. R. Nair (2010)
10.1038/ncomms1489
A polysaccharide bioprotonic field-effect transistor.
Chao Zhong (2011)
10.1038/nnano.2010.279
Single-layer MoS2 transistors.
B. Radisavljevic (2011)
10.1021/nn102598m
Structural defects in graphene.
F. Banhart (2011)
Single‐layer MoS 2 transistors
B Radisavljevic (2011)
10.1038/nnano.2012.162
Selective molecular sieving through porous graphene.
S. P. Koenig (2012)
10.1021/nl3002205
Electron tunneling through ultrathin boron nitride crystalline barriers.
L. Britnell (2012)
10.1021/nl3002205
Atomically thin boron nitride: a tunnelling barrier for graphene devices
L. Britnell (2012)
10.1021/nl3012853
Water desalination across nanoporous graphene.
D. Cohen-Tanugi (2012)
10.1021/nn303869m
Selective molecular transport through intrinsic defects in a single layer of CVD graphene.
S. O'Hern (2012)
10.1126/science.1236686
Ultrathin, Molecular-Sieving Graphene Oxide Membranes for Selective Hydrogen Separation
H. Li (2013)
10.1016/J.CARBON.2013.05.052
Impermeability of graphene and its applications
V. Berry (2013)
10.1039/c3cp52318g
First principles study of the permeability of graphene to hydrogen atoms.
M. Miao (2013)
10.1021/la4018695
Simulation insights for graphene-based water desalination membranes.
Deepthi Konatham (2013)
10.1126/science.1236098
Selective Gas Transport Through Few-Layered Graphene and Graphene Oxide Membranes
H. Kim (2013)
10.1038/ncomms3642
Hopping transport through defect-induced localized states in molybdenum disulphide.
Hao Qiu (2013)
10.1038/nature12385
Van der Waals heterostructures
Andre K. Geim (2013)
VanderWaalsheterostructures
A. K. Geim (2013)
Impermeability ofgrapheneand its applications
V. Berry (2013)
10.1021/nl5006542
Electronic properties of graphene encapsulated with different two-dimensional atomic crystals.
A. Kretinin (2014)
10.1126/science.1249097
Ultimate Permeation Across Atomically Thin Porous Graphene
K. Çelebi (2014)
10.1021/la403969g
Mechanisms of molecular permeation through nanoporous graphene membranes.
C. Sun (2014)
10.1016/J.MATTOD.2014.01.021
Nanoporous graphene materials
W. Yuan (2014)
10.1016/J.CARBON.2013.09.055
Graphene: An impermeable or selectively permeable membrane for atomic species?
L. Tsetseris (2014)
10.1021/nl404118f
Selective ionic transport through tunable subnanometer pores in single-layer graphene membranes.
S. O'Hern (2014)
Mechanismsofmolecularpermeation throughnanoporousgraphene membranes
C. Sun (2014)
Nanoporous graphene materials. Mater. Today
W Yuan (2014)
10.1016/b978-0-12-454135-1.50008-1
Supplementary References
S. Elhage



This paper is referenced by
10.1021/ACSANM.1C00620
Layer-by-Layer Growth of Graphene Sheets over Selected Areas for Semiconductor Device Applications
J. Anguita (2021)
10.1016/J.CEJ.2021.129280
Analyses and insights into 2D crystallite architected membrane electrode assemblies for polymer electrolyte fuel cells
P. Balakrishnan (2021)
10.1007/s10965-021-02434-z
Corrosion properties of organic polymer coating reinforced two-dimensional nitride nanostructures: a comprehensive review
M. Mirzaee (2021)
10.1016/J.JMST.2020.12.084
Review on the corrosion-promotion activity of graphene and its inhibition
Wen Sun (2021)
10.1016/J.DIAMOND.2021.108414
Hydrogen molecules permeate graphene: Permeate way and the breaking and recombination of bonds
Xing-hua Zhu (2021)
10.1021/acsami.0c21495
Heterointerface Effects on Lithium-Induced Phase Transitions in Intercalated MoS2.
Sajad Yazdani (2021)
10.1002/AELM.202001045
Recent Advances in GaN‐Based Power HEMT Devices
Jiaqi He (2021)
10.1038/S41928-021-00548-2
Large transport gap modulation in graphene via electric-field-controlled reversible hydrogenation
Shaorui Li (2021)
10.1016/J.CARBON.2021.02.078
Fabrication and electrochemical response of pristine graphene ultramicroelectrodes
S. Goodwin (2021)
10.1007/s12274-021-3575-9
Towards intrinsically pure graphene grown on copper
Xiaozhi Xu (2021)
10.3390/CRYST11010047
Advances in the Applications of Graphene-Based Nanocomposites in Clean Energy Materials
Y. Xiang (2021)
10.1016/J.NANOMS.2021.05.002
Recent advances in graphene and other 2D materials
P. Ares (2021)
10.1016/J.CARBON.2021.02.056
Permeation of chemisorbed hydrogen through graphene: A flipping mechanism elucidated
M. Bartolomei (2021)
10.1088/2053-1583/abf80f
The stable interfaces between various edges of hBN and step edges of Cu surface in hBN epitaxial growth: a comprehensive theoretical exploration
Leining Zhang (2021)
10.3389/fmats.2021.683503
Uniform Strain-Dependent Thermal Conductivity of Pentagonal and Hexagonal Silicene
Huake Liu (2021)
10.1039/d0nr07384a
Scalable synthesis of nanoporous atomically thin graphene membranes for dialysis and molecular separations via facile isopropanol-assisted hot lamination.
Peifu Cheng (2021)
10.1039/d1nr00307k
Influence of stacking on the aqueous proton penetration behaviour across two-dimensional graphtetrayne.
Zhixuan Ying (2021)
10.1021/ACSENERGYLETT.0C02427
Two-Dimensional Hexagonal Boron Nitride for Building Next-Generation Energy-Efficient Devices
Youning Gong (2021)
10.1016/J.PORGCOAT.2021.106330
Synthesis of poly(p-phenylenediamine) encapsulated graphene and its application in steel protection
Jie Zhang (2021)
10.1088/2053-1583/abe777
Coating performance of hexagonal boron nitride and graphene layers
Xuemei Li (2021)
10.1038/s41578-020-00268-7
Artificial channels for confined mass transport at the sub-nanometre scale
Jie Shen (2021)
10.3390/C7020035
A Review on van der Waals Boron Nitride Quantum Dots
Amitabha Acharya (2021)
10.1002/anie.202105619
A Chemistry and Microstructure Perspective on Ion Conducting Membranes for Redox Flow Batteries.
Ping Xiong (2021)
10.1016/J.COMMATSCI.2021.110335
On the desalination performance of multi-layer graphene membranes; A molecular dynamics study
Mohammad Ali Abdol (2021)
10.1016/J.MEMSCI.2021.119146
Effect of the orientation of sulfonated graphene oxide (SG) on the gas-barrier properties and proton conductivity of a SG/Nafion composite membrane
Chongshan Yin (2021)
10.1016/j.porgcoat.2020.105961
Comparison study on chelated and non-chelated titanate functionalized graphene nanosheets for enhancement of waterborne alkyd anticorrosion coating
Haihua Wang (2021)
10.1038/s41467-020-20503-7
Catalytic activity of graphene-covered non-noble metals governed by proton penetration in electrochemical hydrogen evolution reaction
Kailong Hu (2021)
10.1016/J.CARBON.2021.02.084
High hydrogen coverage on graphene via low temperature plasma with applied magnetic field
Fangzhou Zhao (2021)
10.1039/D1RA00278C
Advantages, limitations, and future suggestions in studying graphene-based desalination membranes
S. Castelletto (2021)
10.1016/j.rser.2020.110660
Overcoming undesired fuel crossover: Goals of methanol-resistant modification of polymer electrolyte membranes
Jing Zhou (2021)
10.1002/ADMT.202001171
A Review of Nanostructured Ion‐Exchange Membranes
M. Shehzad (2021)
10.1039/D1CP02121D
Isotopic separation of helium through graphyne membranes: a ring polymer molecular dynamics study
S. Bhowmick (2021)
See more
Semantic Scholar Logo Some data provided by SemanticScholar